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395 Wellington Street 395. rue Wellington OltawaON KIAON4 Ottawa ON K1A ON4 Canada Canada
Your hie VOrnrmtaraocS
Our nie Norre felmtmw
The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distribute or seil reproduire, prêter, distribuer ou copies of this thesis in microfom, vendre des copies de cette thèse sous paper or electronic formats. la forme de microfiche/nlm, de
reproduction sur papier ou sur format électronique.
The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fiom it Ni la thèse ni des extraits substantiels may be printed or othewise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation.
To my mum and dad, my cheerful skters and brother,
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
such as DTPA or DTMPA, to the peracetic acid solution minimizes the Cu(I1) and Fe(II1)
indud decomposition of peracetic acid but increases the Mn(I1) induced decornposition. The
addition of sodium pyrophosphate eflectively deactivates the metal ions and consequently
improves the bleaching performance.
The peracetic acid consumption in wasteful reactions was quantified by detemining
the gaseous products evolved. It is found that aithough carbon dioxide is fonned under
certain conditions, oxygen is the dominant product of the wasteful reactions. One mole of
oxygen is forme. per two moles of oxidant (peracetic a d and hydrogen peroxide) consumed.
Therefore, 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. 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.
This suggests that the oqgen formation can be used for control of an industrial peracetic acid
treatment.
Finally, a kinetic mode1 of peracetic acid briçhtening of a soivent-assisted ozone
delignified pulp was developed. The model consists of three parallel and one consecutive
reaction, and is based on reaction pathways reported for Iignin model compounds with
peracetic acid. 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.
ACKNOWLEDGEMENT
1 would like to express my deepest appreciation to my thesis s u p e ~ s o r s , Drs. Ni and
van Heiningen, for al1 their help, encouragement and invaluable guidance throughout the
course of this study. Without them this work would not have been possible!
1 wish to thank Mr. M. d'Entremont for his help with some of the experiments.
It is a pleasure to extend gratitude toward a11 the members of the Dr. Limerick Pulp
& Paper Research and Education Centre for their assistance and suggestions during the
course of this work. Special thanks to Le Zeng, XiaoZhu Zhang, Russell Girard, Teik Ooi and
Drs. Kang , Li and Ghosh for al1 the valuable discussions.
Financial support fiom NSERC in the fonn of a Strategic Grant is greatly appreciated.
I also wish to thank Dr. RW. Thring, Mr. & Mrs. Hildebrand, Mr. M. Peters for their
moral support dunng my study in Canada.
My greatest thanks must go to my dear wife, Lizhen, whose love, support,
understanding and encouragement have bolstered me through this endeavour.
BFUGHTENING OF A SOFTWOOD KRAFT PULP DELIGNIFIED BY METHANOLASSISTED
..................................... OZONATION 32
..................................................... Abstract 33
Introduction .. ................................................. 34
Experimental .............................................. 36
Results and Discussion .......................................... 37
Peracetic Acid Brightening (Pa) of ZnEo Delignified Pulp .............. 37
Further Brightening of ZnEoPa Treated Pulp in an Eop Stage .........*. 40
Further Brightening of ZnEoPaEop Treated Pulp by a Final Pa Treatment . . 46
................... Brightness Stability of the TCF Fully Bleached Pulp 46
Chernical Cost Evaluation of the ZnEoPaEop Sequence ................ 46
Conclusions ......................................... . 47
References ................................................... 49
KINETICS OF PERACETIC ACID DECOMPOSITION PART 1: SPONTANEOUS DECOMPOSITION AT TYPICAL PULP BLEACHING CONDITIONS .......... 54
Abstract ..................................................... 55
Introduction .................................................. 56
Experimental ................................................. 59
Approcach ................................................. 60
.......................................... Results and Discussion 62
vii
References ................................................ 68
CHAPTER 5 KINETICS OF PERACETIC ACID DECOMPOSITION PART II: ALKALINE HYDROLYSIS ................. 75
Abstract ..................................................... 76
Introduction ........................................... 7 7
Experimental ................................................. 78 .......................................... Results and Discussion 79
Establishment of Conditions for Determination of Hydrolysis Kinetics ..... 79 .................. Kinetics of the Alakline Hydrolysis of Peracetic Acid 84
Predictions Obtained with the Hydrolysis and Decomposition Kinetics ..... 87
................ Effect of MgSO. on the Consumption of Peracetic Acid 88
Condusions .................................................. 90
References ................................................... 92
CHAPTER 6 THE ROLE OF TRANSITION METAL IONS DURING PEFWCETIC ACID BLEACHING OF
.............................. CHEMICAL PULPS 101
Abstracf .................................................... 102
Introduction ................................................. 103
Experimental ................................................ 104
......................................... Results and Discussion 106
Effect of Additives on the Meta1 Catalysed Decomposition of .............................................. Peracetic Acid 108
The Role of Transition Metal Ions during Peracetic Acid ................................... Bleaching of Chernical Pulps 112
Conclusions ................................................. 117
References .................................................. 119
CHAPTER 7 THE FORMATION OF GASEOUS PRODUCTS AND ITS RELATION TO PULP BLEACHING DURING
.............. TEE PERACETIC ACID TFtEATMENT 129
Abstract . ...................1.....o......................... 130
Introduction ..........................e...................... 131
......................................... Results and Discussion 135
The Formation of Gaseous Products during the Decomposition of .................... ............. .... Peracetic Acid ,. .. 135
The Effect of DTPA and DTMPA on Gas Formation and Peracetic .......................................... Acid Decomposition 138
The Formation of Gaseous Products and Its Relation to Peracetic Acid Bleaching .............................................. 140
Conclusions ................................................. 144
References ........................................... 146
BRIGHTENING OF AN OZONE DELIGNIFIED ........................ SOF'TWOOD KRAFT PULP 160
Abstract .................................................... 161
Introduction ................................................. 162
Experimental ................................................ 163
......................................... Results and Discussion 165
............................... Development of the Kinetic Mode1 166
.................................. Estimation of the Initial Values 171
........................................... Modelling Results 174
Conclusions ................................................. 177
References .................................................. 179
.................................. CHAPTER 9 CONCLUSIONS 191
GeneralSummary ............................................ 192
.............................. Recommendations for Future Work 196
THE COMPUTER OPTIMIZATION PROGRAM FOR THE KINETIC STUDY OF PERACETIC
............................ ACID BRIGHTENING 197
Table 3.1 . The Fractional Factorial Design of b(39 for Pa Brightening of ZnEo Delignified Pulp ........................ 38
Table 3.2 .
Table 3.3 . Table 3.4 .
Table 3-5 . Table 3.6 . Table 3-7 .
Table 4 4 .
Table 4.2 .
Table 5.2 .
Table 5.3 .
Table 6.1.
Table 6.2 .
Table 6.3 .
The Effect of Reaction Time on Peracetic Acid Bleaching .................................. of ZnEo Delignified Pulp 40
The Effect of NaOH Charge on the Eop Stage ................. 41
The Addition of DTPA to the Eop Stage ...................... 43
The Addition of MgSO. to the Eop Stage ..................... 44
The Effect of Temperature and Reaction Time of the Eop Stage ... 45
Estimation of Bleaching Chernical Cost of the ZnEoPaEop Sequence .................................... 47
The Observed Second-order Rate Constant as a Function of pH a t 40°C ................................... 63 Rate Constant of the Spontaneous Decomposition as a Function of Temperature .............................. 66
Rate Constant of the Peracetic Acid Hydrolysis .............................. as a Function of Temperature 87
The Required Time to Convert 95% of Residual ........................ Peracetic Acid to Hydrogen Peroxide 88
The Composition of Magnesium Species in Aqueous Solution a t 40 OC with Varying pH and MgSO. Addition ................ 90
Meta1 Ion Contents of the Materials Used in This Study ........ IO5
Conditional Stability Constants of Metal Ion to DTPA ............................. Complexes a t pH 7.0 and 20°C 109
Peracetic Acid Bleaching of Oxygen Delignified Softwood Kraft Pulp (O Pulp) ............................. 113
Table 6-4. Peracetic Acid Bleaching of Ozone Delignified Softwood Kraft Pulp .................................... 117
Table 7-1. The Formation of Gaseous Products and Its Relation to Bleaching during Peracetic Acid Treatment of an Oxygen Delignified Pulp ................................. 141
Table 8-1. The Development of the Light Absorption Coeficient a t pH 6.0, ............ 50°C and Different Peracetic Acid Concentrations 166
Table 8-2. The Kinetic Parameters Obtained by the Book and Jeeves Search Algorithm at 50°C for the
.................................. Brightening of ZE Pulp 176
xii
Figure 4-1. The effect of stabilizers on the decomposition of peracetic acid at 40°C, pH of 7.0 . . . . . . . . . . . . . . . . . . . . . . . . . , , . 69
Figure 4-2.
Figure 4-3.
Figure 4-4.
Figure 4-5.
Figure 4-6.
Figure 5-1.
Figure 5-2.
Figure 5-3.
Figure 5-4.
Figure 5-5.
Figure 5-6.
Figure 5-7.
Plot of k, versus 2M/(l+M)' at 40°C, pH = 5.5 -9.0 . . . . . . . . . . . . 70
Comparison of the predicted and experimental relationship between &, and pH at 40°C . . . . . . . . . . . . . .. .. . .. . 71 Koubek's plot of Logk, versus pH at 25"C, with 103 m o n EDTA [8] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Ranalysis of Koubek's data 181 with the kinetic mode1 developed in this study at 2s0C, with IO3 m o n EDTA . . . . . . . . . . 73
The Arrhenius plot of the spontaneous decomposition of peracetic acid .. . .. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. . . .. 74
Addition of DTPA or DTMPA on the peracetic acid decomposition a t pH 9.5 and 40°C.. . . . . . .. . . . . . . . . . . . . . . . . . . 94 Addition of DTPA or DTMPA on the peracetic acid decomposition a t pH 8.2 and 40°C. . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Effect of H'O, concentration on the disappearance rate of peracetic acid at pH 8.2 and 40°C . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Effect of pH on the consumption of peracetic acid (40°C, 8.2-12.0 pE,0.5 g/L DTMPA). . . . . . . . . . . . . . . .. . . .. . .. . 97
Determination of the rate constants of the alkaline hydrolysis of peracetic acid (40-60°C, 10.5-12.0 pH, 0.5 g/L DTMPA) . . . . . . . 98 Comparison of determined and predicted peracetic acid and hydrogen peroxide concentrations (pH 9.5, 40°C, 0.5 g / L DTMPA) . . . . . . . . . . . . . . .. . . . .. . . . . .. .. 99
Effect of MgSO, on the consumption of peracetic acid at 40°C and pH of 9.5 . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 100
Figure 6-2.
Figure 6-3.
Figure 6-4.
Figure 6-5.
Figure 6-6.
Figure 6-7.
Figure 7-1.
Figure 7-2.
Figure 7-3.
Figure 7-4.
Stability of a peracetic acid soiution ............. (40°C, pH 7,0,0.75 ppm metal ion concentration) 122
Effect of additives on copper catalysed peracetic acid decomposition (40°C, pH 7.0,0,75 pprn Cu2', 0.5 g/L DTPA, DTMPA or MgSO,, 2 g/L Na,P20,) ......................... 123
Effect of additives on iron catalysed peracetic acid decomposition (40°C, pH 7.0, 0.75 ppm FeY, 0.5 g / L DTPA, DTMPA or MgSO,, 2 g/L Na,P20,). ........................ 124
Effect of additives on manganese catalysed peracetic acid decomposition (40°C, pH 7.0,0.75 pprn Mn2', 0.5 g/L DTPA, DTMPA or MgSO,, 2 g/L Na,P20,) .................. 125
Effect of DTPA on the manganese catalysed decomposition of .... peracetic acid(40°C, pH 7,0,0.75 ppm Mn2', 0-5 g/L DTPA) 126
Effect of DTPA or DTMPA on the manganese catalysed decompositioo of peracetic acid (40°C, pH 5.0,0.75 pprn Mn2', 0.5 g/L DTPA or DTMPA) ................................ 127
Effect of DTPA or DTMPA on the manganese catalysed decomposition of peracetic acid (40°C, pH 6.0,0.75 pprn Mn2', 0.5 g/L DTPA or DTMPA) ................................ 128
The experimentai setup for the determination of gaseous products during peracetic acid decomposition ................ 148
The formation of gaseous products and the consurnption of peracetic acid at 25OC, pH 8.2, F(He) of 100 mumin and with 05 g/l DTMPA addition ............................. 149
The stoichiometry of the peracetic acid consumption and the oxygen formation at 2S°C, pH 8.2, F(He) of 100 mL/min and with 0.5 g& DTMPA addition ......................... 150
Gas formation and the consumption of peracetic acid in the presence of 0.75 pprn Mn(II) and a t 25"C, pH 8.2, F(He)of 100mWmin .................................... 151
Figure 7-6.
Figure 7-7.
Figure 7-8.
Figure 7-9.
Figure 7- 10.
Figure 7- 1 1.
Figure 7-12.
Figure 8-1.
Figure û-2.
Figure 8-3.
the presence of 0.75 ppm Mn(1I) and at 2S°C, pH 5.0, ..................................... F(He) of 70 mumin 152
The stoichiometr-y of peracetic acid consumption and carbon dioxide formation in the presence of 0.75 ppm Mn(U) and a t 25"C, pH 5.0, F(Be) of 100 milmin) ............. 153
Plausible mechanism of the carbon dioxide formation during peracetic acid decomposition ........................ 154
The effect of DTPA addition on peracetic acid consumption and the oxygen formation at 25"C, pH 8.2, F(He) of 100 mumin and with 0.02 moVL DTPA added at 30 min, . ................ 155
The effect of DTMPA addition on peracetic acid consumption and oxygen formation in the presence of 0.75 ppm Mn@) at 2S°C, pH 8.2, F(He) of 100 mumin and with 0.02 m o n
................................. DTMPA added at 30 min 156
The relationship between the wasted peracetic acid and hydrogen peroxide (O or OQ pulp, 40-60°C, pH 5-7,1.5-5% peracetic acid charge, 0.5-1.5% pulp consistency, 30-120 min) . . 157
The relationship between the peracetic acid consumption due to the pulp oxidation and the pulp brightness (O or OQ pulp, 40-60°C, pH 5-7, 1.5-5% peracetic acid charge, 0.5-1.5% pulp consistency, 30-120 min) ............... 158
The relationship between the pulp viscosity and the oxidant consumed in wasteful reactions (O or OQ pulp, 40-60°C, pH 5-7, 1.5-5% peraceticacid charge, 0.5-1.5% pulp consistency,
............................................ 30-120 min) 159
The effect of pH on the Iight absorption coefficient development during Pa brightening of ozone delignified softwood kraft pulp (50°C and [CH3C03H] of 0.0493 moVL) ..................... 183
The proposed kinetic mode1 for peracetic acid brightening ..................... of ozone delignified softwood kraft pulp 184
Estimation of C3, and k, (50°C, pH 7.0, [CH3C03H] of 0.0493 m o n ) .................. 185
Figure 8-5. Cornparison of mode1 predictions and experimental results (50°C, p H 7.0, [CH,CO,H] of 0.0493 moi&) .................. 187
Figure 8-6. Predictions of the development of Cl, C,, C, and C .................. (50°C, pH 3.0, [CH,C03H] of 0.0493 moi&) 188
Figure 8-7. Predictions of the development of Cl, C2, C3 and C .................. (50°C, pH 7.0, [CH3C0,HJ of 0.0493 m o n ) 189
Figure 8-8. Predictions of the development of C,, C,, C3 and C (50°C, pH 10.0, [CH3C0,H] of 0,0493 moüL) ................. 190
xvi
NOMENCLATURE
[c l = chromophore concentration
[CH3C03H], = total titratable peracetic acid concentration, (mol/L)
DTPA = diethylenetriaminepentaacetic acid
DTMPA = diethylenetriarninepentamethylenephosphonic acid
EDTA = ethylenediarninetetraacetic acid
E = alkaline extraction stage
Ea = activation energy, (kcaVmol)
ECF = Elemental Chlorine Free
Eo = alkaline oxidative extraction
EOP = hydrogen peroxide reinforced oxidative extraction stage
EP = hydrogen peroxide reinforced extraction stage
% ISO = international standard organization brightness
k = reaction rate constant
Ka = acid ionization constant
ko = pre-exponential constant
ko, = observed rate constant
k = ionization constant of water
M = the ratio of proton concentration to the dissociation constant
P = hydrogen peroxide bleaching stage
xvii
Q
TCF
Zn
= chelating stase
= Totally Chlorine Free
= solvent-assisted ozone bleaching stage
CHAPTER 1
INTRODUCTION
BACKGROUND
In pnnciple, bleaching of chemical pulps consists of two steps: (1) to remove the
residual lignin, and (2) to brighten the pulp. Oxidants, such as chlorine, chlorine dioxide,
hypochlorite, oxygen, hydrogen peroxide, peracids and ozone, are known as good
delignification andfor brightening chemicals. An aikaline stage is usudly included in the
bleaching process to solubilize the oxidized lignin, and to reactivate the residual lignin for
subsequent bleaching treatments.
New regulations are forcing the pulp and paper industry to reduce the environmental
impact of pulp bleaching. 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.g. MCC or RDH) 11-31 andor oxygen
delignification [4], (2) modifjmg the bleaching process by complete substitution of chlorine
with chlorine dioxide, e.g. the so-called ECF (Elemental ChIorine-Free) process [5,6], and the
adoption of an alkali oxidative extraction stage (Eo) or a peroxide enhanced Eo stage (Eop)
[7,8], (3) (partial) system closure of the bleach plant, such as in the Bleach Filtrate Recycle
process (BFRm) [9].
The ECF bleaching process is now becoming the dominant bleaching technology for
chemical puIps. Totally Chlorine Free (TCF) bleaching processes are also emerging 16, IO].
Ozone, oxygen, hydrogen peroxide and peracids are potential TCF bleaching chemicals.
Among them, hydrogen peroxide and peracids are possible substitutes for chlorine dioxide
in the final brightening stages due to their high brightening capacity [6] .
Peracetic acid, although known as an effective delignifier for nearly fifty years, was
considered too expensive for commercial application. However, recent advances in peracetic
acid production technology have significantly reduced the cost, enabling peracetic acid to
become a promising candidate for pulp bleaching [l 1,131. It has been shown that peracetic
acid can be used as a delignification agent [Il - 181, or as an activation agent for oxygen or
hydrogen peroxide stages [13,19], or as a brightening agent in the final stages of an ECF or
TCF process [l3,19-21 J.
Through earlier studies 122-261, it was demonstrated that a solvent-assisted ozone
process can be used to deligniQ chernical pulps to a low kappa number, while maintaining
good viscosity and strength properties. In order to produce a high strength, high brightness
TCF pulp, one of the objectives of the present project was to develop the subsequent
bnghtening sequence with peracetic acid and hydrogen peroxide.
Sirnilar to hydrogen peroxide, peracetic acid decomposes at pulp bleaching conditions.
Koubek [27] shidied the peracetic acid decomposition in several buffer solutions. However,
since Our preliminary experimental data showed that his kinetics did not accurately predict the
decomposition of peracetic acid at the typical pulp bleaching conditions, the kinetics of
spontaneous decomposition were further investigated in the present work. 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 8.2. Also it is necessary to investigate the
role of transition metal ions during peracetic acid bleaching, which is typically performed at
a neutral pH. Others have found that some of the transition metal ions may catalyse the
decomposition of peracetic acid under acidic conditions (27-3 11. It was also reported 127-
29.3 11 that gaseous products, such as O, and CO, , are formed dunng peracetic acid
decomposition. However, the relationship between the gas formation and the efficiency of
peracetic acid bleaching has not been established. Finally, a kinetic model to describe the
peracetic acid brightening is lackinç.
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 d kraft pu1 ps. More specificall y the objectives
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.
The relevant literature review of peracetic acid decomposition, peracetic acid
bleaching and hydrogen peroxide bleaching is presented in Chapter 2.
In Chapter 3, the inclusion of peracetic acid in a TCF bnghtening sequence for a
Hemlock kraft pulp delignified by a methanol-assisted ozone process is described. The
optimum process conditions for the peracetic acid stage (Pa) and the hydrogen peroxide
reinforced oxidative extraction stage (Eop) are also determined.
The kinetics of spontaneous decomposition of peracetic acid under conditions typical
of pulp brightening by peracetic acid are described in Chapter 4.
In Chapter 5, the effect of pH on the disappearance of peracetic acid in an aqueous
solution is discussed. The alkaline hydrolysis kinetics of peracetic acid are also reported.
The role of transition metal ions during peracetic acid bleaching of chernical pulps is
investigated in Chapter 6. The fundamental phenornena associated with the presence of
additives such as D m DTMPA, Na,P,Q, and MgSO, on the peracetic acid decomposition
and bleaching are examined.
In Chapter 7, the formation of gaseous products and its relation to pulp bleaching
dunng the peracetic acid treatment is studied. 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.
In Chapter 8, 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.
Chapter 9 summarizes the contributions to knowledge resulting fiom this study.
The work describeci in Chapters 3,4,5,6,7, and 8 have been written as self-contained
papers suitable for publication with IittIe or no fürther modifications. Thus each chapter has
its own abstract and references. As far as possible, uniform and standard syrnbols are used
throughout the thesis. The major content of these chapters is goinç to be or has been
submitted or presented at respectively refereed journals and technical conferences.
Specifically :
Chapter 3: Submitted to Papen ja Puu, April, 1997
Chapter 4: The Canadian Joumal of Chernical Engineering, Vol. 75, Feb., 1997, p. 37-4 1
Chapter 5: The Canadian Journal of Chernical Engineering, Vol. 75, Feb., 1997, p. 42-47
Chapter 6: Accepted for publication by Puip & Paper Canada, Feb., 1997
Chapter 7: Submitted to Tappi Joumal, March, 1997
Chapter 8: Submitted to Joumal of Wood Chemistry and Technology, March, 1997
REFERENCES
1. Sjoblom, K., N. Hartler, J. Mjoberg and L. Sjodin, A New Technique for Pulping to Low Kappa Numbers in Batch Pulping: Results of Mill Trial, Tappi J., 66(9):97 ( 1 983)
2. Volk J. 1. and J. J. Young, Successfùl Lo-solidsn' Cooking at Hinton, Preprints the 82* CPPA Annual Meeting, Tech. Sect., CPPA, Montreal, 1996. p. B3 7
3. Andrews, E. K., RDH Kr& Pulping to Extend Deligiification, Decrease Emuent, and Improve Productivity and Puip Properties, Tappi J. 72(11):55 (1 989)
4. van Lierop, B., N. Liebergott, G. Teodorescu, and G . J. Kubes, Oxygen in Bleaching Sequence - an overview, Pulp Paper Can., 87(5): T 193 ( 1986)
Axesard, P., Substituting Chlorine Dioxide for Elemental Chlorine Makes the Bleach Plant Effluent Less Toxic, Tappi J. 69(10):54 (1 986)
Dence, C. W. and D. W. Reeve, Putp Bleaching-Principles and Practice, TAPPl PRESS, Atlanta, Georgia, 1996, p. 4 13
Young, J., G. Start and J. Lazorek, Utilization of an Eop Stage During 100% CIOz Bleaching at Weldwood Hinton, CPPA Pacific and Western Branch AnnuaI Meeting Preprints, Tech. Sect., CPPq Montreat, IW2, Section 4 4 Paper No.3
Anderson, J. R., Hydrogen Peroxide Use in Chemical Pulp Bleaching, 1992 Tappi Bleach Plant Operations Short Course Notes, TAPPI PRESS, Atlanta, p. 123
Ferguson, K. H., Champion Moves Toward Closure with BFR Startup at Canton, N. C., h l p & Paper, 70(4):47 ( 1 996)
Exclusive to Pulp and Paper Canada, No Matter What You Call It, Chlorine-fiee Bleaching 1s Here to Stay, h l p Paper Canada, 90(5):22 (1 992)
Hill, R T., P. B. Walsh, and J. A. HoUie, Peracetic Acid, an Effective Alternative for Chlorine Compound Free Delignification of Kraft Pulp, TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 12 19
Basta, J., L. Holtinger, P. Lundgren, H. Fasten, and R. Fredriksson, Alternatives for Achieving High Brightness TCF Pulps, Proceedings, 1994 International Non-chlonne Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., Amelia Island, FL, sec. 1 1-3
Anderson, J. R, B. Amini and W. Wilkinson, On-site Generation and Use of Peroxy Acids in Chemical Pulp Bleaching, Preprints, 81" CPPA Annual Meeting, Tech. Sect., CPPA, Montreal, 1995, p. B59.
Christiansen, C. B., and W. F. Parker, Laboratory Studies of Acetic Acid Bleaching, Preprint, TAPPI Annual Meeting, 1 965, p. 13 2
Rapson, W. H. and C. B. Anderson, Bleaching in Five Stages to Asymptotic Lirnit Using Only One Oxidant and Sodium Hydroxide, 1985 International Pulp Bleaching Conference Proceedings, Quebec, 1985, p. 227
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, 1 993 Non Chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., HHI, SC, sec. 8-1
Gellerstedt, G., Peracid Technology Review, Preprint, 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology, Raleigh, N.C., March, 1 993
Bailey, C. W. and C. W. Dence, Peroxyacetic Acid Bleaching of Chemical Pulp, Tappi J., 49(1):9 (1966)
Liebergott, N., Peracid Delignification and Bleaching, 1 994 TAPPI Pulping Conference Proceedings, TAPPi PRESS, Atlanta, p. 357
Devenyns, J., F. Desprez and N. Troughton, Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion fiom Conventional Chlorine Bleaching via ECF toTCF, TAPPI 1 993 Pulping Conference Proceedings, T APPI PRESS, Atlanta p. 341
Troughton, N., F. Desprez and J. Devenyns, Peracids: The Pathway to High Brightness TCF Kraft Pulps, Proceedings of 1994 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Arnelia Island, FL, sec. IO- 1
Ni, Y. and A R P. van Heiningen, Ozone Dioxane Bleaching of Chemical Pulps, U.S. Patent 5354423, 1994
Solinas M. and T. H. Murphy, Ozone Selectivity Improved with Use of Organic Solvent, Pulp & Paper, 70(3): 133 (1 996)
Ni Y., A. R P. van Heiningen, J. Lora, L. Magdzinsk and E. K. Pye, A Novel Ozone Bleaching Technology for the Alcellm Process, J. Wood Chem. and Technology, 16(4):367-380 (1 996)
Kan& G. J., Y. Ni and A. R. P. van Heiningen, Mechanism of Cellulose Protection in a Novel and Selective Ozone Pulp Bleaching Process, Prepnnts, 82"' CPPA Annual Meeting Tech. Sect., CPPA, Montreai, 1996, p.B303
Ni, Y. and A. R. P. van Heiningen, Improved Ozone Bleaching by Impreçnation of Chemical Pulps with An Acidified Mixture of 1,4-Dioxane and Water, 1996 International Pulp Bleaching Conference Proceedings, Washington, D.C., April, 1996, p.2 13
Koubek, E., The Kinetics and the Mechanism of the Decomposition of Aliphatic Peroxyacids in Aqueous Solutions, Ph.D thesis, Brown Univ. . 1964
28. Kagan, M. J. and G. D. Lubarsky, The Intermediate Stages of Aldehyde Oxidation, J. Phys. Chem., 39, p.837 (1935)
29. Vrbaski, T. and 1. Brihta,, The Kinetics of Oxidation of Aldehydes to Acids and Acid Anhydrides, Arhiv Za Kemiju, 26, p.267 (1 954)
30. V a s p t p , Ya. M., V. O. Gavenko and 1. A. Garbuzyuk, Influence o f Minera1 Salts on the Decay rate of Peroxyacetic Acid in Aqueous Solution, Ukrainskii Khimicheskic Zhumaf, 55(6):584 (1 989)
3 1. Allen, G. C. and A. Aguilo, Metal Ion Catalysed Oxidation of Acetaldehyde, Advances in Chemistry Senes, 76, p.363 (1 968)
CHAPTER 2
LITERATURE FkEVIEW
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. Recent results have shown that peracetic acid is a low capital
intensive, easily retrofitted and highly selective non-chlorine bleaching agent [l-91.
1.1. Production and Properties of Peracetic Acid
Peracetic acid is the mono-acetyi derivative of hydrogen peroxide. It has a single
acidic proton with a pKa of 8.2 at 25°C [IO]. The most important and widely used method
of production of peracetic acid is the direct, acid-catalysed reaction of hydrogen peroxide
with acetic acid, as shown in Equation (1): - CH3CQH + H202 -- CH3C03H + H20
Since the reaction is reversible, an equiiibnum mixture of the reactants is normally available.
However, pure peracetic acid can be obtained by a vacuum distillation technology in which
excess acetic acid, hydrogen peroxide and sulfùric acid catalyst are removed and recycled
[l,9]. Peracetic acid is reported to be insensitive to impact, but explodes violently when
heated to 110°C [I I l . Peracetic acid is classified as a hazardous substance and its
transportation is restricted by Transporiation of Dangerous Goods (TDG) reçulations [ I I l .
Although peracetic acid is used for chernical syntheses, the scale of consumption in a pulp
bleaching application requires d e and economicai generation of peracetic acid at the mil1 site.
The manufacture of distilled peracetic acid requires the installation of a vacuum still. The
process hazards associated with the distillation of the acetic acid-peracetic acid solution are
related to the detonabifity of concentrated mixtures, and must be considered in the design and
operation of a distilled peracetic acid system [9].
Peracetic acid has a sharp, pungent odour. It has a boiling point of 103°C and a
vapour pressure of 20 rnrnHg at 25°C [Il]. It is a weaker acid than acetic acid. The oxidation
potential of peracetic acid is about 1 . 0 6 ~ with the hdf reaction shown in Equation (2):
CH3C03H + 2H + + 2e- CH3C02H + H20 (2)
The principal hazard of peracetic acid is its corrosive nature, which can cause severe
bums to skin, eyes and body tissue. Contacted areas must be washed immediately with large
volumes of water to avoid tissue damage. Exposure to the vapour causes lachrymation and
possibly lung damage. Long-term exposure to peracetic acid can lead to liver damage,
decreased white bIood count, and lung tumors [Il]. Personal protective equipment should
include a respirator in addition to splash proof goggles, rubber acid suit, and rubber gloves.
1.2. 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. Generdly, three discrete pathways were
identified: sidechain oxidation of a-carbonyl groups by the Baeyer-Villiger mechanism [ 12-
153; aromatic ring oxidation initiated by ortho or para-hydroxylation [ 16- 19 j; and side-chain
epoxidation of alkenes [20].
1.2.1. Baeyer-Villiger reaction
This is a reaction whereby peracids oxidize ketones to esters [21]:
The reaction has been shown [22] to proceed by a mechanism involving nucleophilic
attack of the peracetic acid on the carbonyl carbon, followed by migration of one of the
ketone's alkyl or aryl groups. 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. Aiso it was found that a ketone reacts somewhat slower than an
aldehyde, 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
1.2.2. Epoxidation of alkenes
Alkenes are converted to oxiranes by direct transfer of oxygen as in Equation (4) [20].
The oxirane ring may be opened to give a glycol ester if strong acids are present.
1.2.3. Hydroxylation
The oxidation of phenols and their ethers by peracetic acid is commonly initiated by
ortho and para-hydroxylation reactions [23]. The resulting catechols fonned by the former
reaction are first oxidized to ortho quinones, and then to muconic acids, as shown in Equation
(5) [16,17]. Hydroxylation at the para site gives hydroquinones which are subsequently
converted to p-quinones and then to maleic and fùmaric acid derivatives [I7].
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.
Furthmore, 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), wbich
was later confirmed by Kawamoto et al. [24].
1.3. 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]. Other studies confirmed that
peracetic acid is higldy selective in removing lignin fiom wood [26,27]. The subject has
recently been reviewed by Liebergott [ 5 ] . It has been shown that peracetic acid can be used
as a deIignification agent[ l,6,9,28-321, an activation asent for oxygen or hydrogen peroxide
stages [5,9] and as a briçhteninç agent in the final brighteninç stages of an ECF or TCF
bleaching sequence [2,3,5,9].
Bailey and Dence [28] published a research paper describing the use of peracetic acid
for both delignification and brightening of chemical pulps. It was found that the maximum
brightness gain during peracetic acid treatment of spruce kraft pulp occurred at neutrai pH,
while consistency (3 to 6%) and temperature (50 to 85°C) had little effect on the final pulp
properties. At pH of 7 to 9, the reduction in kappa number obtained with peracetic acid was
essentially similar to that of an equimolar quantity of chlorine. Also it appears that a peracetic
acid (or Pa) treatment at slightly acidic conditions of for exarnple, pH of 2.5 to 3.5, leads to
a good delignification [29,30]. More recent work [1,3 1,321 supports the earlier findings that
peracetic acid is a good delignification agent. For example, 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.
Peracetic atid can dm 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
[3,5]. For exarnple, peracetic acid pretreatment of an unbleached softwood kraft pulp at 1%
Pa charge expressed as H,O, can increase the delignification degree from 35% to 48.9%
during an Eop stage [5]. 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]. Troughton et al. [3] showed that at a total hydrogen peroxide charge of 3% an oxygen
delignified softwood kraft pulp with an initial kappa number of 12.4 can be bleached to a
brightness of 74.8% ISO following a QPP sequence, while a brightness of 82.1% ISO is
obtained by a QPPaP sequence.
Peracetic acid is aIso a good brightening chernical which can be used in the final stages
of a bIeaching sequence [5,33 1. 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 1.07% peracetic acid charge, pH 7, 70°C and 8%
pulp consistency. The viscosity was unaffected. Liebergott [ 5 ] found that CE delignified
sulphite pulps were bleached to 85 - 90% ISO brightness with a peracetic acid charge of
about 1%. Brightening of a soflwood kraft pulp with CIO2 or peracetic acid produced a
brightness of 83% at 0.6% CIO, and 86.5% at 0.45% Pa charge expressed as H202.
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. Thus he concluded that chlorine dioxide and peracetic acid bleaching may be
combined in a single stage, which resulted in a higher brightness gain than either chlorine
dioxide or peracetic acid bleaching alone.
Peracetic acid may also replace hydrogen peroxide in TCF bleachinç processes
[4,5,35,36]. Phillips et al. [35] compared the effect of peracetic acid to hydrogen peroxide in
the sequences of OZEZP and OZEZPa. The resulting pulps had a brightness of 85.9 and
89.1% ISO respectively. A surprising fact was that the Pa bleached pulp showed normal
reverted brightness (87.3%), while the peroxide pulp brightness decreased to 76.9% after 2
hr treatment at 1 0S0C. More recent work [5] showed that a Pa treatment of an OZEZ
bleached softwood kraft pulp at a charge of 1 .O% Pa as H,02 increased the pulp bnghtness
from 81.3 to 92.4% ISO, which is superior to a brightness of 90.1% ISO obtained with a
peroxide stage at a charge of 1 %.
Until recently, the drawback of peracetic acid bleaching was its high manufacturing
cost. AIso it is not sufficiently stable to be shipped or stored for extended periods of time
19,111. Dupont, Eka Nobel and Degussa AG are arnong the companies who are marketing
peroxy acids in the pulp and paper industry [1,8,9].
2. PERACETIC ACID DECOMPOSITION AND HYDROLYSIS AT TYPICAL PULP BLEACHING CONDITIONS
Peracids undergo decomposition and hydrolysis by a variety of reactions which
depend on their structures, temperature, pH and the presence of catalysts, notably transition
metd ions. Under typical peracetic acid bleaching conditions, it is expected that in addition
to the lignin oxidation reactions, peracetic acid may aIso be consumed by three wastefiil side
reactions, namely i) spontaneous decornposition, ii) hydrolysis and iii) transition rnetal
catdysed reactions.
2.1 Spontaneous Decomposition
Peracids decompose spontaneousiy in an aqueous solution to give the corresponding
carboxylic acid and oxygen [ZO]. 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,37-4 11. The rate of disappearance of the peracid, ROOH, is given
b y:
- d[RooH1 = k [ROOH] [ROO -1 dt
When peracetic acid containinç about 4% CH,COO1xOIXH was used, oxygen appeared
predominately (83%) as OIW-O'Y [IO]. This leads to the conclusion that the electrophilic site
is carbonyl carbon rather peroxidic oxygen, as shown in Equation (8) [ l O]:
--
The decomposition kinetics of peracetic acid were first studied by Koubek [l O] over
the pH range of 5.9-10.2 in carbonate, phosphate and borate buffers with
ethylenediaminetetraacetic acid (EDTA) as stabilizer. He found the kinetics to be second-
order in total peracetic acid concentration. The reaction rate at 25°C reaches a maximum of
2.7 x 105 Wrno1.s at pH 8.2, which is also the pKa of peracetic acid. The rate constant
inmeases proportionally with pH until it reaches 7.5 and then decreases proportionally when
the pH is higher than 9.0 as follows:
The above kinetics do not include the pH range of 7.5 to 9.0. Equations (9) and (1 O)
show that two straight-line portions with a dope of +1 and - 1 should be obtained if logk,
is plotted against pH. However, Koubek's data showed that the slopes of the two straight line
sections deviated considerably fiom unity. He explained this by the hypothesis that the systern
was complicated by the metal ion catalysed decomposition of peracetic acid [10]. Later
McDonough [18] investigated the decomposition of peracetic acid in an aqueous solution in
the presence of DTPA, and found that the metal catalysed reaction between peracetic acid and
hydrogen peroxide is stilI considerable when DTPA is present, especidly at a pH higher than
8.0. Based on the experirnental results, he conduded that acid hydrolysis and the reaction of
peracetic acid with hydrogen peroxide were responsible for the deviation. He also found that
the rate constant is lower in an aqueous solution than that in a phosphate buffer. This he
explained with the hypothesis that phosphate may catdyse the hydrolysis of peracetic acid.
Rucker and Cates [42] reported that the peracetic acid consumption in a borate buffer at a
pH range of 7.0 to 8.9 is mainly due to hydrolysis, and not to spontaneous decomposition.
This is due to the fact that borate reacts rapidly with hydrogen peroxide to form
peroxyborates so that peracetic acid hydrolysis is dominant. Therefore, the above literature
shows that hydrolysis should be considered, 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.
2.2. Hydrotysis
Hydrogen peroxide and acetic acid are formed upon hydrolysis of peracetic acid. Thus
there is no loss of active oxysen in reaction (1 1):
CH,CO,H + H20 + CH,CO,H + H,Oz (1 1)
However, hydrolysis represents a decrease in real bleaching power since hydrogen peroxide
is not an effective bleaching agent under typicai peracetic acid bleaching conditions.
Acid hydrolysis of peracetic acid was studied by Bunton et al. [43] and Koubek [ 1 O].
It was found [IO] that acid hydrolysis proceeds by nucleophilic attack of water on the
protonated peracid molea.de, with its rate beinç first order in peracetic acid concentration as
weil as acid concentration.
Aikaline hydrolysis has been the subject of only cursory investigation [ 10,441. D'Ans
and Mattner [44] reported that peracetic acid hydrolysis increases with increasing pH and
MgSO, addition, and becomes the dominant mechanism in a 0.9 moVL NaOH solution at
12°C when the transition metal catalysed decomposition of peracetic acid and hydrogen
peroxide is suppressed. However, the kinetics of the alkaline hydrolysis were not reported.
Koubek [IO] observed that alkaline hydrolysis proceeds at a rapid rate which increases with
increasing pH, but again the kinetics were not given.
2.3 Transition Metal Catalysed Reactions
2.3.1 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]. They found that manganese
catalyses the decomposition of peracetic acid under formation of oxygen, carbon dioxide and
c h o n monoxide. Vrbaski and Brihta [46] reported the effect of cobalt on the decomposition
of peracetic acid. Both studies did not address the kinetics and mechanism of the
decomposition of peracetic acid. Koubek [IO] studied the metal ion catalysed decomposition
of peracetic acid at pH 5.4 in an ammonium acetate buffer. He found that the kinetics were
first-order in the peracetic acid concentration, and that the order of decreasing catalytic
activity was Co(II), Mn(II), Fe (II), and Cu(I1). He also showed that the reaction order in
cobaItous ion concentration varied fiom one at 10" mol/L to one-half at moVL. The
activation energy was found to be 21.6 kcal/mol. He proposed that the decornposition
followed a radical mechanism. Vasyutyn et al. [47] reported that in an aqueous solution of
peracetic acid without pH controt, Mn(I1) is the most harmful metal ion, followed by Co(I1)
and Fe(m). Furthemore, they confirrned that the kinetics are first order with respect to the
peracetic acid concentration. On the contrag, 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. However, the above authors didn't
extend their study to a neutral pH range which is of interest for peracetic acid bnghtening.
The importance of transition metal catalysed decomposition of peracetic acid on the chemical
pulp bleaching efficiency has not been examined. Aiso it is worthwhie to investigate the effect
of additives such as DTPq DTMPA Na,P,û,, and MgSO, on peracetic acid decomposition
and bleaching.
2.3.2 Reaction of peracetic acid with hydrogen peroxide
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. Later several workers [38,4 1,49,50] have reported that hydrogen peroxide
reacts with peracids at a pH above 10 as:
RCO, + Hz02 + RCO; + H20 + 0, (1 2 )
Akiba and Simamura [49] carried out this reaction with ''O labelled peroxybenzoate,
and concluded that the evolved O2 came almost entirely fiom hydrogen peroxide.
McDonough [18] studied the reaction of peracetic acid and hydrogen peroxide in aqueous
solutions at a pH range of 7 to 9.5. The reaction rate was found to increase with increasing
pH. He proposed that there are two reactions between peracetic acid and hydrogen peroxide,
one of which is catalysed by traces of transition metals. Reaction mechanisms were proposed
for these two reactions.
Evans and Upton [SOI examineci the reaction of peracetic acid and hydrogen peroxide
at a pH of I O to I 1. 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, 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. Furthemore, Evans and Upton [SOI found that the reaction between peracetic acid and
hydrogen peroxide is strongly catalysed by transition meta1 ions, and that the cataiytic effect
can be minimized by addition of phosphonc acid chelating agents. 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 8.37.
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, + M"' + H1O - RCO, + (MOH)"' + OH-
R C 0 , - + Hz07 - RCOOH + HO.
HO2' + H' ' 02-- ( 16)
(MOH)"' + O?'' + OH- + Mn+ + Oz ( 17)
2.4. 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 [ 1 O,45,46,48 3. Kagan and Lubarsky [45]
studied the manganese caîalysed decomposition of peracetic acid in both acetic acid and water
solutions. They found that the composition of the gaseous products evolved during the
peracetic acid decomposition was different for the two solutions. Carbon dioxide and oxygen
were the main gaseous products formed in the acetic acid solution and water solution
respectively. 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. Vrbaski and Bnhta [46] investigated the cobalt catalysed decomposition of
peracetic acid in an aqueous solution without pH control, and claimed that the only gas
formed is oxygen. Contrary to this finding, 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 5.4 in an ammonium acetate buffer. Furthemore, Koubek [l O] also
established that roughly 80% of the carbon dioxide formed arises from the acetate ion of the
buffer. The above authors did not extend their study to a neutral pH range, the optimum pH
for peracetic acid brightening [28.33].
3, 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. There has been a growing use
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.
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. Another typical appIication of peroxide is to reinfiorce an alkaline extraction stage (Ep)
or an oxygen reinforcd extraction stage (Eop), 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. It has
been shown that brightness and brightness stability are optimum when hydrogen peroxide is
applied at the end of sequences such as OZP, OZEopP and O(QZ)Q(PO) [53]. Recently,
Devenyns et al. 1541 reported a modified version of hydrogen peroxide bleaching, which is
operated at high consistency, high temperature (r 100°C) and under pressure, the so called
P(0) process. Its commercial application showed an improved bleaching response at a Iower
hydrogen peroxide consumption [55,56].
Some transition metals catalyse the hydrogen peroxide decomposition and contribute
to the formation of hydroxyl radicals, HO- and superoxide anion radicals, 02.- [ 1 11. Although
it has been reported that the presence of low concentrations of these radicai species may
actualIy improve hydrogen peroxide bleaching 1571, it is generally accepted that a high
concentration of such radicais ieads to a poor selectivity and impaired bleaching Alkaline
earth metal (e.g., magnesium and calcium) compounds and sodium silicate appear to reduce
the hydrogen peroxide decomposition when added to an alkaline peroxide stase 1581. These
compounds may form complexes with transition metais to lower their catalytic activities.
Proper management of metal ions is essential to achieve efficient hydrogen peroxide
bleaching. 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]. A Mg/Mn ratio of over 30 is needed for effective
hydrogen peroxide bleaching at a temperature range of 60 to 90°C, and the MgMn ratio must
be higher than 100 if the P(0) process is applied [6 11.
Chelants, which are polydentate ligand molecules, are ofien used in the pulp and paper
industry to minirnize the negative effect of metal ions. Some typical chelants include
ethylenediarninetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA).
DiethyIene triamuiepentamethylenephosphonic acid (DTMPA) has also been show to be an
effective chelant [62].
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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, 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. In this chapter,
a final brightening sequence was developed for this ozonated pulp with a peracetic acid
treatment and an Eop stage.
A fiactional factorial design with four parameters, each perforrned at three levels, was
used to optimize the process conditions of the peracetic acid stage. It was found that a single
peracetic acid stage cm not produce a fùlly bleached pulp with a brightness above 88% ISO.
However, this brightness level is achieved by sequential application of a peracetic acid and
an Eop stage. The effect of operating variables of the Eop stage, such as the caustic charge,
MgSO, charge, temperature and time, were also investigated. 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.
Keywords: peracetic acid brightening, ozone delignified s o b o o d kr& pulp, hydrogen
peroxide, totally chlorine fiee bleaching, brightness, viscosity
INTRODUCTION
Commercial production of TCF fblly bleached softwood kraft and sulfite pulps is now
a reality [l-81. However, these TCF processes still have a number of weaknesses. In most
insiances, the final pulp brightness achieved in these bleaching processes is below 88% ISO,
and generalIy in the range of 80 - 85% ISO [3-5,8]. Furthemore, it appears that the pulp
strength properties, such as the tear index (at the same tensile index), are typically 10 - 15%
lower than those of pulps with equd final bnghtness obtained by conventional chlorine-based
bleaching [3,4,7,8]. 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, these
TCF sequences require oxygen delignification ancilor other extended delignification
techniques, which are capital intensive and generally less selective than the chlorine based
processes.
Earlier studies at the Limerick Pulp and Paper Centre and at MacMillan Bloedel[l 1-
151 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. For example, a well delignifed pulp with a kappa number of 5.8 and a
viscosity of 28.4 mPa.s can be obtained when an unbleached Hemlock kraft pulp with a kappa
number of around 30 and a viscosity of about 33 rnPa.s was subjected to a ZnEo sequence,
where Zn represents the solvent-assisted ozone bleaching stage.
Peracetic acid, although known as an effective deligni fication chemical for nearl y fi@
years- was until recently considered too expensive for commercial application [ 161. However,
recent advances in the manufacture of peracetic acid have significantly reduced the cost,
making peraçetic acid a promisinç candidate for pulp bleaching [16,18]. Most of the literature
on peracetic acid in pulp bleaching deals with delignification [ 1 6,17,2 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. 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. The pulp brightness increased to 85% ISO after 4 hours at a 1.07%
charge of peracetk acid, pH 7,70°C and 8% pulp consistency. A minimum viscosity loss was
observed in the pH range of 8 to 9. Liebergott [19] found that CE delignified sulphite pulps
could be bleached to 85 - 90% ISO brightness with a peracetic acid charge of about 1%.
Brightening of a softwood kraft pulp with C10, or peracetic acid produced a brightness of
83% ISO at a charge of 0.6% CIO,. and 86.5% ISO at a peracetic acid charge of 0.45%
expressed as equivalent weight of hydrogen peroxide [i 91.
Hydrogen peroxide is a good brightening chernical when the optimum conditions are
used [8,29-3 11. 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. It is known
[32,33] that a-carbonyl and quinone structures are effdvely removed, while a, P-unsaturated
double bonds are stable and continuously formed durinç conventional hydrogen peroxide
bleaching. On the other hand, double bonds in residual liçnin are very reactive toward
peracetic acid [34]. Therefore, one might expect that a higher brightness could be achieved
by a sequentiai treatment of chemical pulp with peracetic acid and hydrogen peroxide, as was
confirrned by Liebergott (351 as well as Ni and Ooi [36].
The main objective of the present study was to develop a TCF brightening sequence
usin3 peracetic acid and hydrogen peroxide for the ZnEo sofiwood kraft pulp to produce a
fÙlI brightness, high strength product comparable to conventionally bleached pulp.
EXPERIMENTAL
Peracetic acid was purchased fiom Aldrich (Milwaukee, USA). Its composition is
about 34% w/w peracetic acid, 5% wlw hydrogen peroxide, 40% wlw acetic acid with the
remainder being water. Reagent gade -O2, NaOH, MgSO, and DTPA obtained fiom Fisher
Scientific (Nepean, Ontario) were used without fùrther purification. The quantities of
chernicals are expressed as a weight percentage of pure chernical on oven dried pulp. 2.24%
peracetic acid charge equals to 1% H,O, on an equivalent oxidant basis.
The ZnEo pulp with a brightness of 56.5% ISO, kappa number of 5.8 and viscosity
of 28.4 mPa-s was obtained fiom MacMillan Bloedel Ltd.. The kappa number and viscosity
of the original unbleached Hemlock kraft pulp were about 3 0 and 3 3 mPa.s respectively. 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 ozone charge was 2%, of which
over 90% was consumed during the course of the reaction. The ozonated pulp was then
subjected to an Eo stage at the following conditions: 2% NaOH charge, 205 kPa 0, pressure,
10% pulp consistency, 7OoC, 1 hour. The ZnEo treated pulp has a transition metal ion content
of 61.8 ppm Fe, 2.7 ppm Mn and 1.3 ppm Cu.
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.
M e r Pa treatment, the pulp was washed thoroughIy with deionized water and the spent
liquor was titrated for its residual peracetic acid and hydrogen peroxide concentration
following the iodometric method developed by Greenspan and Mackellar [37].
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. An oil bath was used to keep the bomb at the required temperature.
After the Eop stage, the pulp s l u q was washed thoroughly with deionized water and the
spent liquor was analysai for residual H,O,.
Pulp brightness, viscosity and kappa number were determined in accordance with
TAPPI methods T452 om-92, T230 om-89, and T236 cm-85 or Tappi UM246, respectively.
RIESULTS AND DISCUSSION
1. Peracetic Acid Brigbtening (Pa) of ZnEo Delignified Pulp
The ZnEo semi-bleached pulp was subjected to a peracetic acid treatment (Pa). A
hctiond fadorial design ofh(3') was used to optimize the process conditions. Temperature,
pH, peracetic acid charge and pulp consistency were chosen as the four factors, and each was
investigated at three levels. Table 3-1 Iists the bleaching results &er 3 hr. Also included are
the standard data analysis results, 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.
For example, 1, is the average brightening result obtained at the first level (1%) of the first
factor (peracetic acid charge) at different pHs, temperatures and pulp consistencies; II, is the
average brightening result obtained at the second level (pH 7.0) of the third factor (initial pH)
at different peracetic acid charges, temperatures and pulp consistencies.
Table 3-1. The Fractional Factorial Design of b(3') for Pa Brighiening of ZnEo Delignified Pulp
Bleaching Results I
Run Fa1
Pulp Conc. (%)
IO 1
Pa Charge
(Yo)
1 .O
Initial PH
Temp. (OC)
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. For example, a maximum
brightness difference of 5.6% ISO was obtained between the pulps prepared at different
Brightness (% ISO)
Max. Diff.
Viscosity (mPa.s)
Visco.: Ii
II,
IIIi
M U
25.5
24.7
22.8
initial pH levels of 5.0, 7.0 and 9.0.
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. The optimum pH is in the neutral range, which is consistent with the findings of
eariier studies [ I9,24,28]. Table 3- 1 shows that the pulp brightness increases with increasing
temperature, while the pulp viscosity decreases slightly at the highest temperature. 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
reduced to 14.8 mPa.s. The latter can be attributed to the hct that at higher temperature more
peracetic acid is consumeci in wastefùl side reactions which generate harmful reactive species
(see Chapter 6 for details). Therefore, a temperature of about 60°C is optimum for peracetic
acid brightening of the ZnEo delignified pulp. Table 3-1 also indicates that a peracetic acid
charge of 1.5% is appropriate since the fiirther increase in btightness is very small when the
peracetic acid charge is raised fiom 1.5 to 2%. Finally, an increase in puIp consistency from
10% to 20% improves the bleaching results by an additional 3.3% ISO brightness units.
However, a fbrther increase in consistency to 30% lads to a slightly smaller brightness gain.
This may be explained by the difficulty of mixing pulp and chemicals at 30% consistency.
Based on the above analysis, it can be concluded that the optimum condition for
peracetic acid bnghtening of ZnEo delignified pulp is 1.5% peracetic acid charge, 20% pulp
consistency, 60°C and an initial pH of 7.0. The ZnEoPa pulp produced at these optimum
conditions has the following properties: 82.7% brightness, 26.6 mPa.s viscosity and 1.9
kappa number.
For al1 the runs perfomed so far in this study a reaction time of 3 hours was chosen.
We fùrther studied the efFect of bleaching time at the above specified optimum conditions.
The results listed in Table 3-2 show that there is no need to extend the bleachins time beyond
3 hours. Furtherrnore, it shows that the viscosity loss during peracetic acid bleaching is
relatively smail when operated at the optimum conditions, confirming that peracetic acid is
rather selective dunng final brightening [ 1 7,24,28].
Table 3-2, The Effect of Reaction Time on Peracetic Acid Bleaching of ZnEo Delignified Pulp
Other Conditions: 1.5% Pa charge, 20% pulp consistency, 60°C, initial pH of 7.0
2. Further Bnghtening of ZnEoPa Treated Pulp in An Eop Stage
Bleaching Time ( h o
O
1
2
3
4
In the previous section, it wras shown that the optimum peracetic acid charge is about
1 .5%. 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%. Therefore, we fùrther
treated the ZnEoPa pulp with either an Eo or an Ep or an Eop stage. It was found that an Eop
stage gave the best brightening result. The pulp brightness afler either the Eo or Ep stage was
about 2-3 units Iower than that after the Eop stage. Therefore, the Eop stage was used for
Brightness (% ISO)
56.5
78.2
80.7
82.7
82.9
Viscosity (m Pas)
28.4
27.2
26.8
26.6
26.0
Residual Pa (% on charge)
-
28.9
21.6
15.7
12.4
further brightening of the ZnEoPa pulp, and the determination of the optimum conditions of
this stage is described in the following sections.
2.1 H202 charge
A fùlly bleached pulp of 88.0% brightness and 1 8.9 mPa.s viscosity can be obtained
when subjecting the ZnEoPa pulp to an Eop stage with charges of 0.5% H202 and 1.5%
NaOH. A fiirther increase in the HzOz charge fi-om 0.5% to 1.0% raises the brightness to
89.0°/0, however the viscosity decreased to 15.1 rnPa.s. Therefore, 0.5% H,O, charge will be
used in the Eop stage.
2.2 NaOH charge
It is known that the perhydroxyl ion, the dominant form of H,O, under alkaline
conditions, is the reactive species during peroxide brightening. However, excessive caustic
addition may cause aikali darkening. Therefore optimization of the alkalinity is important for
a maximum brightness gain. The results in Table 3-3 suggest that a NaOH charge of 1 -5%
is the optimum level for the present conditions.
Table 3-3. The Effect of NaOH Charge on the Eop Stage
Other conditions: 0.5% H202 charge, 0.05% MgSO, , 20% consistency, I05"C, 60 psi O, Dressure, 60 min.)
NaOH Charge (% on 0.d. pulp)
0.5
Residual H,O, (% on charge)
26.1
Brightness (% ISO)
85.9
Viscosity (m Pas)
31.1
2.3 DTPA addition
The effect of DTPA addition to the Eop stage was investigated for the ZnEoPaEop
sequence (Table 3-4). As mentioned earlier, a TCF bleached pulp with a brightness of 88.0%
1SO and viscosity of 18.9 rnPa.s was obtained without DTPA in the Eop stage. With a DTPA
charge of 0.2%. the brightness did not change significantiy but the viscosity decreased to 1 6.7
mPa.s. A fûrther increase in the DTPA charge resulted in both a decrease in viscosity and
brightness. Also less residual hydrogen peroxide was present at the end of bleaching when
more DTPA was charged to the Eop stage. Similar results were obsenred for hydrogen
peroxide bleaching of an oxygen delignified kraft pulp [38]. However, 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 [39,40]. 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]. Colodette et a1.[41] found that DTPA
addition to a hydrogen peroxide solution reduces the copper and manganese catalysed
decomposition of hydrogen peroxide, but enhances the iron catalysed decomposition. It was
also reported [42,43] that Fe3' chelated by EDTA or DTPA is still catalytically active
towards hydrogen peroxide decomposition. Therefore, 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. Thus, it is expected that a beneficial effect will be observed if the pulp sample
contains more manganese and copper. However. a negative effect is expected if the iron
content is relatively high in the pulp. In the experimental section, it was reported that iron is
by far the most dominant transition metal species in the ZnEo delignified pulp. This then
explains why in Our system the addition of DTPA has a detrimental effect on the performance
of the Eop stage.
Table 3-4. The Addition of DTPA to the Eop Stage
Other conditions: 0.5% H,O, charge, 1.5% NaOH, 0.05% MgS0, . 20% consistency, IO5OC 60 Dsi 0- m e . 60 min )
i
2.4 MgSO, addition
Residual H202 (% on charge)
20.5
12.1
O
MgSO, is known as a stabiiizer for hydrogen peroxide bleaching [44,45]. 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.s are obtained when 0.05 to O. 1% MgSO, is added to the Eop stage. The cornpiete
consumption of residual hydrogen peroxide in the absence of MgSO, is an indicator of
significant peroxide decomposition and thus less efficient use of hydrogen peroxide for
brightening reactions. The addition of too much MgSO,, however, reduces the brightness
development. 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.
2.5 Temperature and reaction time
The effect of temperature and reaction tirne on the Eop stage is shown in Table 3-6.
Viscosity (mPas)
18.9
16.7
12.1
r
DTPA charge (% on O-d. pulp)
O
0.2
0.4
Brightness (% ISO)
88.0
88.3
84.3
0.6 84.0 10.6 O
A cornparison of pulps with similar brightness (Run 2 and 5) shows that a decrease in
Table 3-5. The Addition of MgSO, to the Eop Stage
II Other conditions: 0.5% H,O, charge, 1.5% NaOH, 20% consistency, 105"C, 60 psi Q 11 pressure, 60 min.)
Residual H,02 (% on charge)
O
20.5
27.3
temperature fiom 105°C to 9S°C improves the Mscosity by about 2 to 3 units. Note also that
more hydrogen peroxide remains at 95OC than at 10S°C, indicating that less hydrogen
peroxide is decomposed during bleaching at 95°C. To compensate for the decrease in reaction
rate at a lower temperature , the reaction time of the Eop stage at 95°C was extended fiom
60 to 90 minutes. A hrther increase in the reaction time to 90 minutes at 105°C or to 120
minutes at 95°C deçreased the final Mscosity. Therefore the optimum reaction time should be
about 90 minutes at 95°C.
2.6 The optimum Eop condition
B a d on the above reported results it is now possible to define the optimum operating
conditions of the Eop stage for the ZnEoPa treated pulp: 0.5% H,0, ,1.5% NaOH and 0.1%
MgSO,, 95OC, 20% consistency, 60 psi oxygen pressure and 90 minutes. No DTPA is needed
for this particular pulp since iron is the dominant transition rnetal ion present in the pulp. The
Viscosity (mPa.s)
12.2
18.9
19.9
MgSO, charge (% on 0.d. pulp)
O
0.05
O. 1
Brightness (% ISO)
84.4
88.0
88.2
0.2
0.4
87.5
87.1
19.5
19.0
17.2
15.3
final brightness and viscosity for these conditions are 88.1% 1SO and 2 1.8 mPa.s.
Table 3-6. The Effect of Tempenture and Reaction Time of the Eop Stage
-
Other conditions: 0.5% H,O, charge, 1.5% NaOH, 0.1% MgSO, . 20% consistency, 60 psi 0, pressure
2.7 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.s or
higher. Therefore, 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. Unfortunately. due to insufficient sample, the strength
properties of this TCF fully bleached pulp could not be determined. 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. Another characteristic of
Residual H20, (% on charge)
3 1.3
27.3
O
49.1
Brightness (% ISO)
86.5
88.2
89.1
86.5
Viscosity (mPa.s)
19.4
19.9
15.4
22.6
the present TCF sequence is that no chelants are used in the bleachinç sequence.
3, Further Brightening of the ZnEoPaEop Treated Pulp by a Final Pa Treatment
As show in Section 2.1, the brightness of the ZnEoPaEop pulp was limited to about
89%. However, the brightness can be further increased by a find Pa treatment at a charge of
0.5% while the other conditions being the same as those of the first Pa stage. The resulting
bleached pulp has a brightness of 90.4% ISO and a viscosity of 20.5 rnPa.s. 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.
4. Brightness Stability of the TCF Fully Bleached Pulp
TCF firlly bleached pulp samples of 88.1 and 90.4% ISO brightness obtained by the
ZnEoPaEop and ZnEoPaEopPa sequence respectively, were subjected to rapid aging at
105OC for 1 hour. The brightness reversion of both pulps was about 1.1% ISO, which
compares favourabiy with a reversion of 1.9% ISO for a conventionally chlorine and chlorine
dioxide bleached pulp [ 1 O].
5. 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 88.1% 1SO and a
viscosity of 21.8 mPa.s. Table 3-7 shows that the total cost of the bleaching chemicals used
in the process is about 55 US.$ per tonne of pulp. This is comparable to that of an ECF
bleaching process [ 3 6 ] .
Table 3-7. Estimation of Bleaching Chernical Cost of the ZnEoPaEop Sequence
1 Total chemical cost (U.S.$/ton 0.d. pulp) 55-82 I From reference [5 1 ]
Stage
Zn
Eo
Pa
EOP
Other chernicai costs From reference 1201
CONCLUSION
Chernicals
0 3
NaOH
0 2
Peracetic acid
NaOH
H A
MgSO4
A conventional sofiwood kraft pulp with kappa number of 30 has been bleached to
88% ISO brightness while maintaininç a viscosity of more than 20 mPa.s by a ZnEoPaEop
TCF sequence with 2% ozone, 1.5% Pa and 0.5% hydrogen peroxide charge. The brightness,
Cost (U-S.$)
22.0
6.0
0.6
17.7
4.5
4.5
0.53
Charge (% on 0.d- puIp)
2.0
2.0
1 .O
1.5
viscosity and brightness stability of this TCF filly bIeached kraft pulp are similar to or better
Unit Price (U,S.%/kg)
1.1.
0.3
0.06
1.18
t han those of chlotine-containing bleached pulp.
This chapter focuses on the final brightening of ZnEo pulp by peracetic acid and
1.5
0.5
O. 1
hydrogen peroxide. The optimum conditiom for the peracetic acid and Eop stages have been
0.3
O. 9
O. 53
determined. Those for the Pa stage are 20% pulp consistency ,60°C, a neutral pH and 3 hours.
The peracetic acid charge for the first and second Pa stage is 1.5% and 0.5% respectively.
The optimum conditions for the reinforced Eop stage are 20% pulp consistency , 95"C, 60
psi oxygen pressure, 90 min with 0.5% H202 , 1.5% NaOH and 0.1% MgSO,. The unique
charactenstic of this TCF sequence is that it can be applied to conventional sofiwood kraft
pulp with a kappa number of about 30 . Also, no chelation chernicals are required for this
TCF bleaching sequence.
ACKNOWLEDGMENT
The author thanks NSERC for financial support in the form of a Strategic Grant and
MacMillan Bloedel Ltd. for supplying the ZnEo pulp.
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CHAPTER 4
KINETICS OF PERACETIC ACID DECOMPOSITION
PART 1: SPONTANEOUS DECOMPOSITION AT
TYPICAL PULP BLEACHING CONDITIONS
ABSTRACT
Peracetic acid is one of the alternative non-chlorine bleaching chernicals for
production of fiilly bleached chemical puips. In this paper, the stability of peracetic acid was
studied in an aqueous solution under conditions most likely encountered in industry. It was
found that three reactions, narnely i) spontaneous decomposition, ii) hydroiysis and iii)
transition metal catalysed reactions, are potentially responsible for the consumption of
peracetic acid. Furthemore, the kinetics of the spontaneous decomposition were developed.
It was found that the reaction follows second-order kinetics with a maximum rate at pH 8.2,
which is the pKa of peracetic acid. The developed kinetic equation provides a very good
description of the experimental results obtained in this study.
Keywords: kinetics, peracetic acid, spontaneous decomposition, hydrolysis, pulp bleaching
INTRODUCTION
Environmenta1 concems and market pressure are forcing the pulp and paper industry
to explore alternatives to conventionaI chlorine bleaching. Recent results have s h o w that
peracetic acid is a less capital intensive, easily retrofitted and highly selective Total Chlorine
Free (TCF) bleaching agent when used under optimum conditions [ Il.
Peracetic acid is the mono-acetyl derivative of hydrogen peroxide, and has a single
acidic proton with a pKa of 8.2 at 25°C [SI. It is usually prepared by mixing acetic acid and
hydrogen peroxide with sulfùric acid added as a catdyst [3]. Since the reaction is reversible,
an equilibrium mixture of reactants and products is normally available. High purïty peracetic
acid can be obtained by distillation.
Peracetic acid decomposes spontaneously in an aqueous sohtion to give acetic acid
and oxygen [3]. Transition metal ions such as cobalt and manganese catalyze peracetic acid
decomposition. However, the catalytic effect can Mrtuaily be eliminated by the addition of
a suitable chelating agent [Z]. In addition, peracetic acid cm be hydrolyzed to form hydrogen
peroxide and acetic acid [33. Since hydrogen peroxide and oxygen are ineffective bleaching
agents under typical peracetic acid bleaching (Pa) conditions, both the decomposition and the
hydrolysis are undesirable. Therefore, a better understanding of the mechanism and kinetics
of peracetic acid decomposition and its hydrolysis is of findamental importance for a
commercial Pa stage.
There are a few studies reporied in the literature on the decomposition kinetics of
peroxyacids. 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.
Recently, Francis et al. [ 5 ] reported a kinetic study of the decomposition of caro's acid under
conditions more similar to those encountered during pulp bleaching, and confirmed that the
decomposition follows a second order dependence on the total caro's acid concentration.
However, Francis et al. [ 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 lads
to an increase in the decomposition rate by a factor of 10.
The decomposition kinetics of peracetic acid were first studied by Koubek et al. 121
over the pH range of 5.9-10.2 in carbonate, phosphate and borate buffers with
ethylenediaminetetraacetic acid (EDTA) as stabilizer. He found that the dependence of the
kinetics on the total peracetic acid concentration is second-order. The reaction rate at 2S°C
reaches a maximum of 2.7 x 1 V3 Umo1.s at pH 8.2, which is the pKa of peracetic acid. The
rate constant increases proportionally with pH until it reaches 7.5, and then decreases
proportionalIy with pH when the pH is higher than 9.0.
A mechanism of peracetic acid decomposition was proposed which is compatible with
the above kinetics. It was postulated that the decomposition reaction involves a nucleophilic
attack of a peracid anion on a peracid molecule as:
However, 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. Also, we found that at a pH higher than 8.2, the peracetic acid hydrolysis is not
negligible, and therefore a correction must be made to account for the peracetic acid
consumption due to hydrolysis. Furthemore, Koubek's kinetics did not include the pH range
fiom 7.5 to 9.0. The presence of buffers in his study, which leads to an increase in the ionic
strength of the solution, might influence the decornposition rate of peracetic acid, similar to
that observed by Francis et al. [SI when they studied the kinetics of caro's acid
decomposition. In addition, the presence of buffer solutions may change the nature of how
peracetic acid is consumed, as was found by Rucker and Cates 163. They reported that the
peracetic acid consumption in a borate buEer in the pH range of 7.0 to 8.9 is mainIy due to
hydrolysis and not spontaneous decomposition. 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 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. In this chapter, the kinetics of spontaneous decomposition of peracetic acid
are reported in a pH range of 5.5 to 9.0. In the next chapter, the effect of pH, stabilizers and
hydrogen peroxide on the decomposition of peracetic acid as well as the kinetics of the
peracetic acid hydrolysis will be discussed.
EXPERIMENTAL
Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fkom Aldrich
(Milwaukee, USA). The equilibrium peracetic acid consists of about 34% peracid, 5%
hydrogen peroxide, 40% acetic acid with the remainder being water (al1 in mass%). Reagent
grade MgSO, and DTPA fiorn Fisher Scientific (Nepean, Ontario) and DTMPA from
Buckman (Memphis, USA) were used in the experirnents without fùriher purification . Ail the
experiments were carried out in a 500 mL four-neck round-bottom flask immersed in a
constant temperature bath. The flask was cleaned by washing successively with glassware
cleaner , deionized water, 5% (w/w) sodium hydroxide solution and finally distilled and
deionized water.
The aqueous solution containing al1 required chernicals except peracetic acid was
preheated to the desired temperature. The reaction was initiated by addition of the
concentrated peracetic acid soIution to the reaction flask. The initial peracetic acid
concentration was always 3.75 g/L (equivalent to 1.5% charse on oven dried pulp at 20%
bleaching consistency). The pH was controlled at a constant value by an automatic titrator
through addition of 10 N NaOH . Samples were withdrawn at predetermined time intervals
and analysed in accordance with the iodometric method deveioped by Greenspan and
Mackellar [7]. Ail reported values were the results of at least duplicate experiments.
APPROACH
In the pH mse of 5.5 to 9.0, peracetic acid may be consumed in the following three
reactions:
1. Spontaneous decomposition:
2 CH3C03H - 2 CH3C02H + O,
3 .Transition metai catalyzed reactions:
In the spontaneous decornposition (Reaction (l)), peracetic acid is decomposed to form acetic
acid and O,, thus representing a loss in oxidation power. In Reaction (2), peracetic acid is
hydrolyzed to form acetic acid and hydrogen peroxide. This reaction becomes more important
as the alkaiinity of the solution increases 181. Since hydrogen peroxide at neutral pH is not
reactive in terms of bleaching pulp, Reaction (2) is also considered a wastefiil reaction.
Finally, the presence of transition metals in a peracetic acid solution may induce fûrther
decompositions as indicated by Reactions (3) and (4). The experimental strategy of this
project is to eliniinate the transition metal catalysed reactions by choosing an appropriate
chelating agent. In addition. by measuring both the peracetic acid and hydroçen peroxide
concentrations during the course of the reaction, it is possible to determine the peracetic acid
consumed in both spontaneous decomposition and hydrolysis respectively.
The effect of the addition of a chelating agent on the consumption rate of peracetic
acid at pH 7.0 is shown in Figure 4-1, where the intesral form of the kinetics for a second-
order reaction is plotted versus reaction time 191. For the blank system one can observe that
afler an initial linear behaviour the integral form increases faster than the reaction tirne.
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. The latter is a
confirmation of the second order behaviour of the kinetics in total peracetic acid
concentration. The reduced consumption of peracetic acid with the chetant addition may be
attributed to the transition metai catdyzed reactions, Le., Reactions (3) and (4). It was found
that a concentration of 0.5 g/L diethylenetriaminepentaacetic acid (DTPA) or diethylene
triaminepentarnethylenephosphonic acid (DTMPA) is sufficient to give reproducible second-
order rates at pH of 5.5 to 7.5. The fact that DTPA gives the same result as DTMPA
indicates that at this pH range both DTPA and DTMPA are effective cheiating agents.
However, as the pH inaeases further t O the range of 7.5 t O 9.0, we found t hat only DTMP A
is an efficient stabilizer while DTPA is not. Therefore, at a pH of 7.5 to 9.0, O. 5 g/L DTMPA
was added to the peracetic acid solution to eliminate the transition metal catalyzed reactions.
As report4 earlier [SI, the peracetic acid hydrolysis increases at a higher pH. It was
found that at pH 8.2 the hydrogen peroxide concentration after 2 hours at 40°C is about 9%
higher than the initial hydrogen peroxide concentration. This accounts for about 4% of the
total peracetic açid consumption in accordance with the stoichiometry of Reaction (2). Since
hydrogen peroxide is very stable at the present conditions, the increase in the hydrogen
peroxide concentration can be used to quanti@ the extent of peracetic acid hydrolysis
(Reaction (2)). Thus it can be concluded that the peracetic acid hydrolysis is negligible in the
pH range of 5.5 to 8.2 since the hydrogen peroxide concentration remained almost constant.
At pH 9.0 and 40°C, about 15% of the peracetic acid is consumed after 2 hours due to
hydrolysis. However, with the hydrolysis kinetics developed in next chapter the disappearance
of peracetic acid cm be corrected for the hydrolysis so that the spontaneous decomposition
rate of peracetic acid can be determined over the pH range of 5.5 to 9.0 under othenvise
commercial peracetic acid bleaching condition.
RESULTS AND DISCUSSION
Using the approach described above, the obsewed second-order rate constant k, was
obtained fiom the dope of straight line plots of the reciprocal of the total peracetic acid
concentration [CH,CO,H], , versus time. As s h o w in Table 4- 1, k,, increases with pH up
to the pK, of the peracetic acid of 8.2 183. This is in agreement with Koubek's results in
carbonate and phosphate buffers. As the pH increases beyond 8.2, Table 4- 1 shows that k,
is decreased. As discussed above, k, at pHs of 8.5 and 9.0 in Table 4-1 is corrected for
peracet ic acid hydrolysis.
The second-order kinetics in total peracetic acid concentration ( [CH,CO,H], ) for
spontaneous decomposition in the pH range of 5.5 to 9.0 can be written as :
where the total peracetic acid concentration is the sum of both undissociated and dissociated
peracetic acid, i.e. :
[CH,CO,H], = [CH3C03H] + [CH,CO,']
Table 4-1. 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,H + CH,CO; + H '
with K,=[CH,CO;J w+]/[CH,CO,H].
Rearrangement of the equilibrium constant yieIds:
[CH,CO,HJ/[CH,COJ = CH+]& = M (8)
where M is a constant at fixed pH and temperature. By combining Equations (6) and (8) one
obtains:
[CH,COJ = [CH,CO,H](( 1 +M)
and [CH,CO,H] = M [CH,CO,H] J( I +M)
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. Therefore,
the rate equation becomes:
In tems of disappearance rate of total peracetic acid, the rate equation is:
Substitution of Equations (9) and (1 0) into Equation (1 2) yields:
By comparing Equation (5) with Equation (13), it is obvious that k, is related to the rate
constant of spontaneous decomposition, k, as:
When the pH is 8.2, i.e. at the pKa of peracetic acid, the ratio of the proton concentration to
the dissociation constant, M, is equal 1. As a result, k, reaches its maximum, and Equation
(14) reduces to k, = 0.5k .
The rate constant of the spomaneous peracetic acid decomposition, k, can be obtained
from Equation (14) by plotting k, versus 2M/(1 + M ) ~ . This plot is shown in Figure 4-2 for
the data obtained at 40°C . As discussed earlier, since the peracetic acid hydrolysis becomes
important when the pH is higher than 8.2, the two data points at a pH of higher than 8.2 have
been corrected using the kinetics of the peracetic acid hydrolysis.
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,
k, . The good agreement between the experimental and predicted values of 16, as a function
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. 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
9.5. 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). 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)), but does not eliminate them
entirely. 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 9.5 where the rate of spontaneous
decomposition is relatively low.
Using the data analysis technique descnbed above, the rate constant, k, at 25, 35 and
60°C were obtained. They are Iisted in Table 4-2 together with the experimental data of k,
at pH of 8.2. A cornparison of k and k, confirms that k,, = 0Sk which is predicted by
Equation (1 4). Furthemore, compareci with a 16, of 2.7 x 1 O-3 Umo1.s at 25°C and pH of 8.2
obtained by Koubek [SI, one cm see that the presence of buffers in Koubek's study increases
the spontaneous decomposition rate by a factor of about 2.
The activation energy of the spontaneous decornposition can be obtained fiom the
Arrhenius plot s h o w in Figure 4-6. An activation energy of 22.5 kcaVmol is found. This
compares with an activation energy of 30.0 kcal/mol reported by Koubek [SI for the
spontaneous decomposition of peracetic acid in carbonate and phosphate buffers. However
this value can only be considered as an estimate since his experimental data was influenced
by the transition metal catalysed reactions.
Table 4-2. Rate Constant of the Spontaneous Decomposition
Therefore, the rate of spontaneous decomposition of peracetic acid can be written as:
as a Function of Temperature
where [CH3COjm is the total peracetic acid concentration; T is the temperature in degrees
Kelvin and M is the ratio of the proton concentration to the dissociation constant of peracetic
acid.
CONCLUSION
The stability of an aqueous solution of peracetic acid has been studied under typical
puIp bleaching conditions. The consumption of peracetic acid without the presence of pulp
occurs via three routes: i) spontaneous decornposition; ii) hydrolysis; iii) transition metal
catalyzed reactions. The addition of chelating agents, such as DTMPA, can effectively
eliminate the third reaction route. In the pH range of 5.5 to 8.2, the hydrolysis is negligible
and the peracetic acid consumption is mainly due to spontaneous decomposition, whiIe
h, at pH 8.2 Temperature ("C) l
k
between pH of 8.2 to 9.0, the peracetic acid consumption is due to both spontaneous
decomposition and hydrolysis.
The kinetics of the spontaneous decomposition of peracetic acid were fùrther studied.
It was found to be second-order with respect to the total peracetic acid concentration
([CH,C03w), and that the maximum rate occurs at a pH of 8.2, the pKa of peracetic acid.
Based on the earlier mechanism proposed by Koubek 181, 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. The activation energy is 22.5 kcahol . The present kinetic equation gives a very good
description of the experimental results obtained in this study.
ACKNOWLEDGMENT
Financial support fiom NSERC in the fom of a Strategic Grant is greatly appreciated.
REFERENCES
Troughton, N. A.. F. Desprez and J. Devenyns, Peracids: The Pathway to High Brightness TCF Kraft Pulps, Proceedinçs of 1994 International Non-chlorine Bleaching Conf, Sponsored by Puip & Paper and Engineering TechnologyTransfer Inc. ArneIia Island, FL, March 6- 10, (1 994), sec. 1 0- 1
Koubeiq E., M. L. Haggett, C. J. Battaglia, K. M. Ibne-Rasa, H. Y. Pym, and J. O. Edwards, Kinetics and Mechanism of the Spontaneous Decomposition of Some Peroxoacids, Hydrogen Peroxide and r-butyl Hydroperoxide, J. Amer. Chem. Soc., 85,2263-2268 (1 963)
Swem, D. E., Organic Peroxides, VoL.1, John Wiley and Sons, New York, 1970, p.362
Bali, D.L. and J. O. Edwards, The Kinetics and Mechanism of the Decomposition of Caro's Acid, 1, J. Amer. Chem. Soc., 78, 1 125- 1 129 (1 956)
Francis, R.C., X. Zhang, P. M. Froass, and 0. Tamer, Aikali-and Metal-induced Decomposition of Peroxymonosulfate, Tappi J., 77(6): 133 (1 994)
Rucker, J. W. and D. M. Cates, 2,2' -bipyridine Catalysed Bleaching of Cotton Fibers with Peracetic Acid Part 1, Textile Res. J., 58(13): 148 (1 988)
Greenspan, F. P. and D. G. MackeUar, Analysis of Aliphatic Per Acids, Analy. Chem., 20, 1061- 1 O63 (1948)
Koubek, E., Ph.D thesis, The Kinetics and the Mechanism of the Decomposition of Aliphatic peroxyacids in Aqueous Solutions, Brown University , New York, (1 964)
Levenspiel, O., Chernical Reaction Engineering, znd Ed., John Wiley & Sons, New York, 1972
-Blank d B l a n k + 0.5 g/L DTMPA
-= t +Blank + 0.5 g/L DTPA
Time (min)
Figure 4-1. The effmt of stabilhers on the consumption of peracetic acid at 40°C, pH of 7.0
Figure 4-2. Plot of 16, versus 2M/(l+M)' at 40°C, pH = 5.5 -9.0
4.0 i Exnerimental Data -- - - - - . - - . - - - - - - - - - 4 r e d i c t e d from k,=2M W(l +M)~
4 . 5 I I I f t
Figure 4-3. Cornparison of the predicted and experimental relationship between bbS and pH at 40°C
Figure 4-4. Koubek's plot of hgkba versus pH at 2S°C, with IOa m o n EDTA [S]
Figure 4-5. Reandysis of Koubek's data [8] with the kinetic mode1 developed in this study at 25T, with 10J moVL EDTA
Figure 4-6. Arrhenius plot of the sponbneous decomposition of peracetic acid
CHAPTER 5
KINETICS OF PERACETIC ACID DECOMPOSITION
PART LI: ALKALINE HYDROLYSIS
ABSTRACT
The consumption of peracetic acid in an aqueous solution was studied. It is shown
that three reactions are responsible for the disappearance of peracetic acid, namely i)
spontaneous decomposition, ii) hydrolysis and iii) transition metal catalysed reactions. The
spontaneous decornposition reaches its maximum at pH 8.2, while both the hydrolysis and
metal ion catalysed reactions increase as the pH increases. At pH 10.5 or higher, the
hydrolysis becomes dominant when the rnetal ion catalysed reactions is minimized by the
addition of DTMPA. Therefore the kinetics of peracetic acid hydrolysis were determined at
the latter conditions. 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. Finally it was found that the addition of MgSO, at pH 9.5 leads to the
formation of a precipitate of Mg(OH), which reduces the rate of transition metal catalysed
reactions, but enhances the rate of hydrotysis of peracetic acid.
Keywords: kinetics, peracetic acid, hydrogen peroxide, decomposition, hydrolysis, transition
metal ions
INTRODUCTION
Peracids, such as peracetic acid and monoperoxysulfûric acid (Caro's acid), are
presently considered as alternatives for conventional chlorine containing chernicals in an effort
to develop more environmental friendly bleaching processes. A number of technical papen
have been published which deal with the application of peracetic acid, Caro's acid. or their
mixture in the delignification stage and final brightness stages [I-41. However, fundamental
knowledge of interest for the application of peracids, such as the stability of peracetic acid
under vanous bleaching conditions, is still incomplete. In chapter 4, we reported on the
kinetics of the spontaneous decomposition. in this chapter. the stability of peracetic acid as
a function of pH and the presence of chelants as well as its hydrolysis kinetics will be
discussed.
D'Ans and Mattner [6] reported that the hydrolysis of peracetic acid increases with
increasing pH and MgSO, addition, and becomes the dominant degradation route in a 0.9
moUL NaOH solution at 12°C when the transition metal catalysed reaction of peracetic acid
and hydrogen peroxide is suppressed. However. the kinetics of the alkaline hydrolysis were
not established. Koubek [7J included the effect of pH on the peracetic acid decomposition
in his doctoral snidy. Furthemore, he confirmed that the hydrolysis of peracetic acid is
enhanced at a higher alkaii concentration.
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. [9] . Both spontaneous and catalytic decomposition paths for
Caro's acid were observed. The spontaneous decomposition increases with increasing pH up
to 9.4, the pKa value for the peroxidic proton of Caro's acid, while the catalytic
decomposition is more pronounced at a higher pH.
A review ofthe Iiterature showed that the kinetics of alkaline hydrolysis of peracetic
acid are not yet established. Therefore, the objective was to develop the kinetics of peracetic
acid hydrolysis. Furthemore, the interaction between peracetic acid and hydrogen peroxide,
its dependence on pH and the effect of the presence of chelants, such as diethylenetriarnine
pentaacetic acid (DTPA) and diethylenetnaminepentamethylene phosphonic acid (DTMPA),
were studied.
EXPERIMENTAL
Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fiom Aldrich
(Milwaukee, USA). The equilibrium peracetic acid consists of about 34% peracid, 5%
hydrogen peroxide, 40% acetic acid with the remainder being water (al1 in mass%). Ragent
grade H202, DTPA and ethanot fiom Fisher Scientific (Nepean, Ontario), and DTMPA from
Buckman (Memphis, USA) were used in the experiments without fiirther purification. All the
experiments were camed out in a 500 mL four-neck round-bottom flask immersed in a
constant temperature bath.
An aqueous solution containing al1 required chernicals except peracetic acid was
mixed and preheated to the desired temperature. The reaction was initiated by addition of
the concentrated peracetic acid sohtion to the reaction flask. The pH was controlled at a
constant value by an automatic titrator through the addition of I O rnol/L NaOH. Samples
were withdrawn at predetemined time intervals and analysed following the iodometric
method developed by Greenspan and Mackellar [IO]. Ail reported values are the result of at
least duplicate experiments.
RESULTS AND DISCUSSION
Establishment of Conditions for Determination of Hydrolysis Kinetics
Since it was reported [6,8,9,1 13 that trace amounts of transition metal ions, such as
cobalt, manganese, copper and iron, catalyse the decomposition of peroxy acids, the effect
of the addition of metd chelants such as DTPA and DTMPA on the stability of peracetic acid
waç first studied. The results at 40°C and pH 9.5 are presented in Figure 5- 1. Also included
is a control experiment without the addition of any chelants, and an experiment perFormed in
the presence of a large concentration of a radical scavenger, in this case ethanol.
It can be seen that the addition of DTPA, with or without the presence of ethanol,
leads to a more rapid and extensive loss of peracetic acid than that obtained in the control
experiment. However, the presence of 0.5 glI DTMPA results in a strong reduction in the rate
of disappearance of peracetic acid, while the hydrogen peroxide concentration now increases.
DTMPA is known to be a very good chelant, with metal binding properties better than DTPA
[14]. As a result, it is reasonable to assume that the disappearance of peracetic acid is only
due to Reactions (1) and (Z), respectively spontaneous decomposition and hydrolysis.
2 CH3C0,H -, 2 CH,CO,H + O, (1 )
CH3C03H + H20 -, CH,CO,H + H70, ( 2 )
Further evidence for this assurnption will be presented in the later part of this chapter. Also,
the increase in hydrogen peroxide concentration (by 27% after 3 hours) can only be explained
by hydrolysis (Reaction (2)).
As noted above, the peracetic acid consumption rate in Figure 5- 1 is higher with the
addition of DTPA than that in the control experiment. As explanation it is proposed that the
catalytic effect of transition metal ions can not entirely be eliminated by the presence of
DTPA. A similar explanation was given by Koubek [7]. In addition, 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. This reaction then may account for the fact that with the addition of
0.5 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.
Most likely, there are two types of transition metal ion catalysed reactions which lead
to the consumption of peracetic acid, in both the control experiment and the experiment with
the presence of DTPA:
In the fint reaction only peracetic acid is involved. As proposed by Koubek [7], the
Mn@), Co@), Fe@) and Cu(II) catalysed decomposition of peracetic acid proceeds through
a radical chah mechanism. The overall reaction is represented by Reaction (3).
M "+
2CH $0 3H - 2CH 3C02H + 0 2 (3)
Both peracetic acid and hydrogen peroxide are involved in the second reaction.
Several workers have reported that the reactions between peracids and hydrogen peroxide
are catalysed by transition metal ions [8,15- 181. 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. The overall reaction [ 181 could be written as:
It was also reported [S. 181 that a direct, uncatalysed reaction between peroxy acids and
hydrogen peroxide (i.e. without transition metal ion catalysis) may take place as:
RCO; + HzOz -+ RCO; + H 2 0 + 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].
However, 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. It was fiirther tested the peracetic acid consumption due to Reaction (5) by increasing
the initial hydrogen peroxide concentration from 0.612 g/L to 2.612 g/L. In the presence of
DTMPA at 40°C for both pH 8.2 and 9.5 it was found that the consumption rate of peracetic
acid was not affected by this more than 4 fold increase in hydrogen peroxide concentration.
Therefore, it cm be concluded that Reaction (5) is negligible under these conditions.
As discussed, Reactions (3) and (4) may proceed through radical pathways.
Therefore, one would expect that the presence of radical scavengers, such as alcohol, wîll
suppress these reactions, and result in a lower disappearance rate of both peracetic acid and
hydrogen peroxide. This was tested by following the peracetic acid and hydrogen peroxide
concentrations in a 30% w/w ethano1 solution with 0.5 g/L DTPA present. Frorn the results
shown in Figure 5-1, it can be observed that the presence of 30% w/w ethano! increases the
stability of both peracetic acid and hydrogen peroxide. This fùrther confims that Reaction
(4) is partialiy responsible for the consumption of both peracetic acid and hydrogen peroxide
at the present conditions.
The addition of DTPA and DTMPA on the consumption rate of peracetic acid was
fùrther studied at a pH of 8.2 and 40°C. The results are presented in Figure 5-2. Again, with
0.5 g/L DTMPA present, the disappearance rate of peracetic acid is the slowest, and the
hydrogen peroxide concentration increases by 9% after 2 hours. The formation of less
hydrogen peroxide in this case compared to that at pH 9.5 (27% increase) can be explained
by the fact that the peracetic acid hydrolysis, Reaction (2), is more pronounced at a higher
pH, as will be dernonstrated later. Comparison of Figure 5-2 with Figure 5- 1 also shows that
with 0.5 g/L DTPA addition, both peracetic acid and hydrogen peroxide are more stable at
pH 8.2 than at pH 9.5. This can be explained by a decrease in both Reactions (3) and (4) with
decreasing pH, 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 9.26-1 1.65 than that at 6.04-8.37. However, it is also possible that the oxidation of DTPA
by peracetic acid at pH 8.2 is not as extensive as that at pH 9.5 [ 151. Comparison of the two
control experiments in Figures 5- 1 and 5-2 reveals that at pH 9.5 the initial consumption rate
of both hydrogen peroxide and peracetic acid are higher than those at pH 8.2. This again can
be explained by the fact that Reaction (4) is favoured at a higher pH. However, since
hydrogen peroxide is the limiting reactant in Reaction (4). The importance of this
decomposition route becomes smail as the hydrogen peroxide concentration approaches zero.
Therefore, the higher consumption rate of peracetic acid in the later phase of the reaction at
pH 8.2 than that at pH 9.5 for the two control experiments rnust be due to the fact that the
spontaneous decomposition is much faster at pH 8.2 than that at pH 9.5 [5,7].
We examined Reaction (4) again by increasing the hydroçen peroxide concentration
fiom 0.612 g/L to 2.6 12 g/L. The results obtained at pH 8.2 and 40°C are plotted in Figure
5-3 according to second-order reaction behaviour with respect to the peracetic acid
concentration. Only in the presence of 0.5 g/L DTMPA is a straight-line behaviour obtained,
confirming that the disappearance rate of peracetic acid at pH 8.2 is dominated by
spontaneous decomposition in Reaction (1) (see Chapter 4). It can also be seen that the
increase in hydrogen peroxide concentration fiom 0.6 12 g/L to 2.6 1 2 g/L in the presence of
0.5 g/L DTMPA does not affect the reaction rate. 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. However, the increase in initial hydrogen peroxide concentration
from 0.612 g/L to 2.612 g/L leads to a substantial increase in the disappearance rate of
peracetic acid when DTMPA is replaced by DTPA. The behaviour can be explained by
insufficient suppression of the metal ion cataiysed reactions (Reactions (3) and (4)) by DTPA,
and that a higher hydrogen peroxide concentration favours Reaction (4). 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).
The effect of pH on the consumption of peracetic acid at 40°C in the presence of
DTMPA is show in Figure 5-4. Since the metal ion catalysed reactions (Reactions (3) and
(4)) are minimized, peracetic acid is consumed either by spontaneous decomposition
(Reaction (1)) or hydrolysis (Reaction (2)). With the increase in hydroçen peroxide
concentration resulting from Reaction (2). the contribution of each of reactions (1 ) and (2)
to the overall consumption of peracetic acid can be calculated. At pH 8.2, about 96% of
peracetic acid is consumed via Reaction (1) after 2 h; at pH 9.5, the peracetic acid
consumption due to Reaction (1) is about 80% after 2 h. At pH 10.5 and 12.0, Reaction (1)
is negligible, while the peracetic acid consumption is almost fully accounted for by the
increase in hydrogen peroxide concentration.
Kinetics of the Aikaline Hydrolysis of Peracetic Acid
After establishment of the appropriate reaction conditions described above, the
kinetics of peracetic acid hydrolysis at pH 10.5 to 12.0 in the presence of 0.5 g/L DTMPA
were determined. First it was confinned that the DTMPA concentration does not affect the
reaction rate, since the results obtained at a DTMPA concentration of 2 g/L were identical
to those at a DTMPA charge of 0.5 a. The integral method was used to analyse the kinetic
data at constant pH and temperature. It was found that the hydrolysis of peracetic acid is
first-order in total peracetic acid concentration, [CH,CO,H],, as:
- d [CYCO3HI
dt = k, ~CH,CO,Hl,
where the total peracetic acid concentration is the sum of concentrations of both
undissociated and dissociated peracetic acid, i. e.
[CH,CO,H], = [CH3C03H] + [CHJOJ
The dissociation of peracetic acid is controlled by the equilibrium:
CH3C0,H s CH3C0, + H *
with K,=[CH,CO,'] [H+]/[CH3C03H]
Rearrangement of the equilibrium constant yields:
with M being a constant at a fixed pH and temperature. By combining Equation (IO) with
(8), one obtains :
Since the mechanism of 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 comparing Equation (1 5) with Equation (7), it is obvious that k, is related to the rate
constants, k, and k, as:
Substitution of M = [H']/K, and [OH'] = Y, /[H+] into Equation (17), followed by
mathematicai rearrangement yields:
This equation can be used to obtain the rate constants k, and k, by plotting k0&, +[H'])/K,
versus KJ[H+]. The results at pHs of 10.5, 11.0, 1 1.5 and 12.0 and temperatures of 40, 50
and 60°C are shown in Figure 5-5. It will be assumed that the effect of temperature on K, is
negiigible over the narrow range of temperatures fi-om 40 to 60°C, while the dependence of
& on temperature was taken into account. It is evident that a straight line relationship exists
between k,,& +w])/K, and KJH']. The slope and the intercept of straight lines,
represent the rate constants k, and k, respectively, and are given in Table 5-1.
The activation energies of the hydrolysis (Reactions (1 3) and (14)) obtained fi-om the
corresponding Arrhenius plots of the data shown in Table 5-1 are 14.9 and 1 1.7 kcaVmol,
respect ively .
Table 5-1. b t e Constant of Peracetic Acid Hydrolysis as a Function of Temperature
Therefore. the hydrolysis rate of peracetic acid can be expressed as:
Prediction Obtained with the Hydrolysis and Decomposition Kinetics
k2 ( Wmo1.s )
7.38
14.5
Temperature ( OC )
40
50
We fûrther tested the above kinetic expression by comparing the predicted and
k, ( L/mol.s )
0.00934
0.0206
experimentally determined peracetic acid and hydrogen peroxide concentrations. The results
obtained at pH 9.5.40°C and 0.5 g/L DTMPA are shown in Figure 5-6. At these conditions,
peracetic acid is consumed either by spontaneous decomposition, whose kinetics were
reported earlier [5], or by hydrolysis. Therefore, 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.
It was proposed [2] that peracetic acid and hydroçen peroxide bleaching can be used
in a sequence without washing , the so called (PaP) sequence. Usually, a significant amount
of peracetic acid is present at the completion of the peracetic acid treatment. Thus, it is
expected that upon addition of caustic and hydrogen peroxide to continue the (PaP) sequence,
the residual peracetic acid wilI be hydrolysed to hydrogen peroxide. With Equation (1 9), the
time required to convert 95% of the residual peraceiic acid to hydrogen peroxide in the (PaP)
stage can be predicted. As an exarnple, the following conditions were taken: 1.5% peracetic
acid charge, 12% pulp consistency and 33% of residual peracetic acid, and an initial pH of
1 1 .O &er addition of caustic. The results are show in Table 5-2. It can be concluded that at
80-90°C the hydrolysis of peracetic acid to hydrogen peroxide is very fast.
Table 5-2. The Required Time to Convert 95% of Residual Peracetic Acid to Hydrogen f eroxide
The Effect of MgSO, 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]. In the present study the effect of
magnesium sulfate addition on the consumption of peracetic acid at 40°C and a pH of 5.0 to
9.5 in the absence of chelants was investigated. It was found that the addition of MgSO, up
90
3.2
Temperature ("C)
Time to hydrolyse 95% of the residuai ~eracetic acid (min)
70
23.4
60
67.4
80
8.4
to concentrations as high as 6 g/L has no effect on the peracetic acid consumption at pH 8.2
or lower. However, at pH 9.5, the peracetic acid consumption does change with the addition
of more than 2.0 p/L MgSO,. althouçh a MgSO, concentration of Iess than 0.5 g/L has a
negligible effect as s h o w in Figure 5-7. It is proposed that at pH 9.5 and a MgSO,
concentration of less than 0.5 g/L, the consumptions of both peracetic acid and hydrogen
peroxide are mainly due to transition metal catalysed reactions. However, the dominant
mechanism changes as the MgSO, concentration increases. Thus, at 2 g/L MgSO, both the
hydrolysis and the transition metal catalysed reactions are important, while at 6 g L MgSO,
the hydrolysis is dominant. 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. A further increase in the MgSO, concentration to 9 g/L enhances the hydrolysis
of peracetic acid.
The following two mechanisms have been proposed to account for the observed
stabilisation effect of MgSO, on an alkaline hydrogen peroxide solution: (a) transition metals
are absorbed and deactivated by the magnesium hydroxide precipitate [20,21]; (b)
stabilization of superoxide anion radicals by Mg'. thereby reducinç the propagation of the
fiee radical chah decomposition reaction [22,23]. The same two mechanisms were considered
in the present study to explain the effect of MgSO, on the peracetic acid consumption. Table
5-3 lists the concentration of solid maçnesium hydroxide upon MgSO, addition as calculated
from the sdubility product of Mg(OH), [24,25] at 40°C. It appears that at pH 8.2 or lower,
no Mg(OH)? precipitate cm be formed if the MgSO, concentration is less than 94 g/L, which
explains why at pH 8.2 or lower, the addition of MgSO, has no effect on the peracetic acid
consumption. However, at pH 9.5 the arnount of precipitated Mg(OH)Z increases rapidly with
increasinç MçSO, addition. The close correlation between the precipate formation of
Mg(OH), and the peracetic acid consumption mechanism provides strong support that the
stabilizing effect of MçSO, is the absorption and deactivation of transition rnetals by a
precipitate of Mg(O& . The above results also explain that at practical bleaching conditions
performed in the neutrd pH region the addition of MgSO, will not improve peracetic acid
bleaching .
Table 5-3. 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. At pH 8.2, both peracetic acid and hydrogen
peroxide are rapidly consumed in three reactions, namely spontaneous decomposition,
hydrolysis and metal ion catalysed reactions. Addition of chelants, such as DTMPA, DTPA,
suppresses the metal ion catalysed reactions and thus improves the stability of both peracetic
acid and hydrogen peroxide. When the pH is higher than 8.2, the spontaneous decomposition
decreases while both the hydrolysis and the metal ion catalysed reactions increase. With
DTMPA present at pH 10.5 or higher, the spontaneous decomposition and metal ion
catalysed reactions are negligible compared to hydrolysis. The kinetics of peracetic acid
hydrolysis were developed at the latter conditions. I t was found that the hydrolysis follows
a first-order behaviour with respect to the total peracetic acid concentration [CH,CO,H],. The
rate expression is given by Equation (1 9).
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.
Finally it was found that the MgSO, addition at pH 9.5 leads to formation of a
precipitate of Mg(Om which reduces the rate of transition metal catalysed reactions but
enhances that of the hydrolysis of peracetic acid. With 6 g/L MgSO, addition at pH 9.5, the
hydrolysis is mainly responsible for the consumption of peracetic acid.
ACKNOWLEDGMENT
Financial support fiom NSERC in the fonn of a Strategïc Grant is greatly appreciated.
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McDonough, T. J. M., Ph.D Thesis, Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Alkaline Solutions, University of Toronto, Toronto, Canada (1 972)
Goodman, J. F. and P. Robson, Decomposition cf Inorganic Peroxyacids in Aqueous Alkali, J. Chem. Soc., 278 1-2875 (1 963)
Akiba, K. and 0. Simamura, Decomposition of Sodium Peroxybenzoate in Sodium Hydroxide Solution, Tetrahedron, 26,25 19-253 1 ( 1 970)
Evans, D. F. and M. W. Upton, Studies on Singlet Oxygen in Aqueous Solution, Part 3, J. Chem. Soc., Dalton Trans., 1 15 1 - 1 153 (1 985)
Rapson, W. H., M. Wayrnan and C. B. Anderson, Hydrosulphite and Peroxide Bleaching of Nine Pure Species Groundwoods, Tappi J., 48(2): 1 13 (1965)
Sjostrom, E. and 0. Valttila, Inhibition of Carbohydrate Degradation during Oxygen Bleaching, Papen ja Puu, 54(11):695 (1 972)
Ericsson, B. B., O. Lindgren and 0. Theander, Factors lnfluencing the Carbohydrate Degradation under Oxygen Aiakiine Bleaching, Svensk Papperstidn, 74:75 7 ( 1 97 1 )
IsBell, H. S. and H. L. Frush,, Carbohydr. Res. 59:C25 (1977)
Colodette, J. L., S. Rothenberg, and C. W. Dence, Factors Mecting Hydrogen Peroxide Stability in the Brightening of Mechanical and Chemimechanical Pulps, Part III: Hydrogen Peroxide Stability in the Presence of Magnesium and Combination of Stabilizers, JPPS, 15(2):545 ( 1989)
anon, CRC Handbook of Chernistry and Physics, 72 nd Edition, C RC Press Inc., Ann Arbor, USA, p.8-43 (1 992)
Stephen, H. and T. Stephen, Solubilities of Inorganic and Orsanic Compounds, Oxford Pergamon Press, New York, Macmillian, No.583,1963
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
A -P CH,CO,H. Control -0- H202. Control
2 -I- CH,CO,H. 0.5 glL DTPA -0- H,O,. 0.5 g/L DTPA O
-0- CH,CO,H. O S glL DTMPA * H,0,. 0.5 g1L DTMPA
0.00 1 I I I
O 20 40 60 1 I
80 100 120
Time (min)
Figure 52. Addition of DTPA or DTMPA on the peracetic acid decomposition at pH 8.2 and 40°C
h - -6 0.5 glL DTPA. 2.612 g/L H,02 O 70 - -U- 0.5 glî DTPA, 2.6t 2 gii H202, 10% w/w EiOH
-31t- 0.5 giL DTPA, 2-61 2 giL H,O,, 30% wlw ELOH
w -1- 0.5 g/L DTPA, 0.61 2 giL H,O, 60- -0-0.5 g lL DTMPA, 0.612 g1L H,O,
9 - - v - O . S ~ K D T M P A . ~ . ~ ~ ~ ~ ~ H , O ,
O 50-
O 40- e
O 1 O 20 30 40 50 60
Time (min)
Figure 5-3. Effect of H,O, concentration on the disappearance rate of peracetic acid at pH 8.2 and 40°C
Figure 5-5. Determination of the rate constants of the alkaline hydroIysis of peracetic acid (40-60°C, 10.5-12.0 pH, 0.5 g/L DTMPA)
Predicted [CH,CO,H] or [H,O,] m Determined [CH,CO,H] - o Deîermined [H,O,]
7
5 û ô O 7 0 8 û
Time (min)
Figure S. Cornpanson of determined and predicted peracetic acid and hydrogen peroxide concentrations (pH 9.5, 40°C, 0.5 g/L DTMPA)
O I O 20 30 40 50 70
Time (min)
Figure 5-7. Effect of MgSO, on the consumption of peracetic acid at 40°C and pH of 9.5
CHAPTER 6
TRANSITION METAL ION CATALYSED DECOMPOSITION OF PERACETIC
ACXD AND ITS EFFECT ON THE CHEMICAL PULP BLEACHING
ABSTRACT
Peracetic acid (Pa) has emerged as a potential alternative for chlorine containing
chemicals used for bleaching of chemical pulps. WhiIe transition metal ions have received
much attention dunng alkaline peroxide bleaching, limited results are available with respect
to their consequences in peracetic acid treatment. In this chapter, we further exarnined the
role of transition rnetal ions such as manganese, iron and copper during the course of
peracetic acid bleaching. Oxygen delignified and ozone delignified softwood kraft pulps were
used. The fûndamental phenornena associated with the presence of additives such as DTPA,
DTMPA, Na,P,O,, and MgSO, 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. As expected, a close relationship
between peracetic acid decomposition and pulp brightness development was observed and
codmed at constant bleaching conditions . A chelation pretreatment stage for pulp with high
metal ion contents, especially manganese, leads to an improved subsequent peracetic acid
bleaching. The addition of sodium pyrophosphate effectively deactivates the metal ions and
consequently improves the bleaching performance. However, the addition of some chelants,
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.
Keywords: peracetic acid bleaching, transition metal ions, decomposition, chelation
INTRODUCTION
Peroxy acids, such as peracetic acid (Pa) and rnonoperoxysulphuric acid (Px), have
recently been identified as promising alternatives to chlorine containing chemicals for
bleaching of chernical puIps [ 1-9 1. The impact of transition metai ions on alkaline peroxide
bleaching has been addressed extensively [ IJ O- 163. It is believed 11 I,14- 163 that these metal
ions catalytically decompose peroxide, leadins to Iess effjcient bleaching, while the radical
species generated in the decomposition reactions result in more carbohydrate degradation.
Management of transition metals is therefore crucial in hydrogen peroxide bleaching [ 1 0- 1 61.
On the other hand, studies on the influence of metai ions on peracetic acid decomposition are
rather scarce. Koubek [ I 71 studied the metal ion catalysed decomposition of peracetic acid
at pH 5.4 in the absence of pulp fibres, and found that it obeyed first-order kinetics in
peracetic acid concentration, and the order of decreasing catalytic activity is Co', Mn2+, Fe2+,
and Cu2+. Vasyutyn [18] reported that in an aqueous solution of peracetic acid without pH
control Mn2+ is the most hamiful metal ion followed by Co2+ and Fe)', and confimed that the
kinetics are first order with respect to the peracetic acid concentration. On the contrary,
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. The above authors did not extend their study to neutral pH, the range which is of
interest for peracetic acid bleachin~ of pulps.
Our project is airning to gain fiindamental understanding of peracetic acid bleaching,
including peracetic atid decomposition reactions. As discussed in Chapters 4 and 5, peracetic
acid may be consumed in i) the spontaneous decomposition, ii) hydrolysis, and iii) the
transition metal ion catalysed decomposition [17,20-211. The mechanism and kinetics of the
spontaneous decomposition were studied before [17]. In Chapter 4, we established the rate
expression for the spontaneous decomposition under the typical peracetic acid bleaching
conditions. In Chapter 5, we reported the kinetics for the hydroiysis and the pH effect on the
peracetic acid decomposition mictions. In this chapter, we investigated the metaf ion induced
peracetic acid decomposition at a pH range of 5.0 to 7.0. The effects of additives such as
DTPq DTMPA, Na,P,O,, and MgSO, on the metal ion induced peracetic acid
decornposition were studied by adding known arnounts of transition metal ions to the
equilibrium peracetic acid. The underlying mechanisms were proposed, and the results were
related to peracetic acid bleaching of both oxygen delignified and ozone delignified softwood
kraft pulp.
EXPERIMENTAL
Equilibnum peracetic acid and ultra-pure grade NaOH were purchased fiom Aldrich
(Milwaukee, USA). The equiIibrium peracetic acid consists of about 34% w/w peracetic acid,
5% W/W hydrogen peroxide and 40% wlw acetic acid with the remainder being water.
Reagent grade chernicals, DTPA from Fisher Scientific (Nepean, Ontario) and DTMPA fiom
Buckman (Memphis, USA) were used in the experiments without fùrther purification. The
following sdts were used in the experiments: FeCI, CuS0,- MnSO, and CoSO,. Distilled and
deionized water was used in a11 experiments. Its metal ion content was below the detection
limits of the atomic absorption (AA) spectroscopic analysis method used in this study.
An oxygen delignified softwood kraft pulp of 37.7% ISO brightness, 13.8 kappa
number and 23.4 mPa-s viscosity was used in this study. 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]. The ozone charge was 1.8% (by weiçht on 0.d.
pulp) of which 90% was consumeci. A subsequent alkali extraction stage (E) was perfonned
at pH 11.0,77"C, 10% pulp consistency for 45 minutes. The properties of the ZnE pulp were
53.8% ISO brighmess, 5.1 kappa number and 22.8 mPa-s viscosity. Chelation (Q) with 0.5%
DTPA was done at 50°C, pH 5 .O, 2.5% pulp consistency for 30 min. The metal ion contents
of the pulps and chemicals determined by AAS analysis are shown in Table 6- 1.
Table 6-1. Meta1 Ion Contents of the Materials Used in This Study
ZnE Pulp
ZnEQ Pulp 1 0.40 -- -
O Pulp 1 61.5
OQ Pulp 1 2.95
40% DTPA 1 0.80 - - -
80 g/L DTMPA 1 0.10
Equilibrium Peracetic Acid 1 <0.01
Peracetic acid decomposition experiments were camed out in a 500 mL four-neck,
round-bottom flask immersed in a constant temperature bath. The aqueous solution
containing al1 the required chemicals except peracetic acid was preheated to the desired
reaction temperature. The reaction was initiated by addition of a concentrated peracetic acid
solution to the reaction flask. The pH was kept constant with an automatic titrator by addition
of 10 moVL NaOH. 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. M e r the Pa
treatment, 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. The bleaching expenments at constant peracetic acid concentration were
conducted in a 500 mL four-neck, weii stirred, round-bottom flask at 1.5 % pulp consistency.
Preliminary bleaching runs were carried out to determine the rate of peracetic acid
consumption. Subsequentiy, the desired amount of peracetic acid was charged to the reaction
mixture at regular time intervals to maintain a constant peracetic acid concentration.
Pulp brightness, viscosity and kappa number were determined in accordance with
TAPPI methods T452 om-92, T230 om-89, and T236 cm-85, respectively.
RESULTS AND DISCUSSION
1.The Transition Meta1 Catalysed Decomposition of Peracetic Acid
We first studied the systern in the absence of pulp fibres. The effect of 0.75 ppm each
of Cu". Fe3+ and Md' additions on the stability of a peracetic acid solution at pH 7.0 is
presented in Figure 6-1. Cobalt was not included due to its negligible amount present in the
chemical pulps as shown in Table 6- 1. Obviousiy, the presence of these metal ions enhances
the peracetic acid decomposition, i.e. are responsible for the so called metal ion induced
/catalysed decomposition [ 171. Note that not only peracetic acid but also hydroçen peroxide
consumption rates are much higher when metal ions are added.
A number of reactions may lead to the consumption of peracetic acid in the presence
of metal ions:
Only peracetic acid is involved. As proposed by Koubek [17], the Mn", CoZ+, Fe2'
and Cu2+ catalysed decomposition of peracetic acid proceeds through a radical chah
mechanism. The overall reaction can be writen in Equation (1):
Both peracetic acid and hydrogen peroxide are involved. McDonough [20) and
Evans and Upton [24] studied the transition metal catalysed reaction of peracetic acid and
hydrogen peroxide, and proposed that the reaction proceeds through a radical mechanism in
which the perhydroxyl radicals are involved. The overall reaction [24] is:
CH3C03H + H202 -' CH3C02H + H,O + 0,l (2)
Our data suggests that redox reactions also take place. For example, we found that
permanganate is generated and then consumed during the course of the reaction when 0.75
ppm Mn2+ (as MnSO,) was added. MnO,' is produced fiorn the oxidation of ~ n " by
peracetic acid as described in Reaction (3). This is supported by the observation that
peracetic acid may oxidize Mn2+ to MnO; [23,25]. Permanganate, in tum, reacts with
hydrogen peroxide and is reduced to Mn2+ (Reaction (4)). 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. The overall reaction shows that peracetic
acid reacts with hydrogen peroxide to form oxygen:
5 CH,CO,H + 2 ~ n " + 3H,O - 2 MnOi + 6H' + 5 CH3CO2H (3)
2 MnO, + 6H' + 5 H202 - 5 O1 1 + 2 ~ n ' + + 8H20 (4)
CH,C03H + 40- -' CH,C02H + H20 + O2 T (2)
We fùrther confirmed the above oxidation-reduction cycle by the addition of MnO,
instead of Mn2+ to the equilibrium peracetic acid solution, and found that the rates of the
peracetic acid and hydrogen peroxide consumption are similar to those with the addition of
~ n " . It should be pointed out that in the absence of trace amount of these metal ions,
Reaction (2) is extremely slow under the condition studied.
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. Magnesium sulfate
is usually added to oxygen delignification and peroxide bleaching to rninimize carbohydrate
degradation andlor peroxide decomposition [30]. Tetrasodium pyrophosphate (Na,P20,) was
also reporteci as a good stabiliser for alkaline peroxide solution [3 11 and peracetic acid [2 Il.
Therefore, in this study we investigated whether the presence of additives, including DTPA,
DTMPA, MgSO, and Na,P20, can rninimize the metal ion induced peracetic acid
decomposition. The results at pH 7.0 and 40°C are presented in Figures 6-2, 6-3 and 6-4 for
the addition of 0.75 ppm each of copper, iron and rnanganese respectively.
We can observe in al1 three cases that the addition of tetrasodium pyrophosphate
stabilises the peracetic acid solution. We fbrther confirmed that the rates of peracetic acid and
hydrogen peroxide decompositions in the presence of Na,PIO, can be adequately predicted
with the kinetics of the spontaneous decomposition developed in Chapter 4, supporting that
the metal ion induced decomposition is neçligible with the addition of Na,P20,. As expected,
the addition of magnesiurn sulfate does not affect the rate of oxidant consurnptions under this
condition, which is in agreement with our finding in Chapter 5.
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,P,O, was
present. 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).
DTMPA is even stronger cheiant than DTPA [27]. The DTPA or DTMPA complexed copper
or femc ion is largely unreactive towards metal ion induced decomposition reactions. 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.
Table 6-2. Conditional Stability Constants of Metal Ion to DTPA Complexes at pH 7.0 and 20°C [32]
Metal Ion 1
In an earlier study [20] on bleaching of groundwood pulp with peracetic acid,
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. He found that the oxidation occurs rapidly in a pH range of 6- 10 and
established that the stoichiornetry is 3 moles peracetic acid per mole of DTPA. Furthemore,
it was found [ZO] that in spite of its susceptibility to rapid oxidation, DTPA can still stabilise
a peracetic acid solution. The metal ion content in the solutions was not quantitatively
deterrnined. In Figures 6-2 and 6-3, 0.5 g/L of DTPA (1 mmoVL) was present. If the sarne
stoichiometry holds, the peracetic acid concentration decrease due to oxidation of the DTPA
should be about 3 rnrnol/L. 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. The effectiveness
of DTPA in stabilizing peracetic acid solutions, despite its susceptibility to oxidation, rnight
be explained by the assumption that chelation occurs much faster than oxidation, so that a
small amount of metal ions present in the reaction solution may be immediately chelated upon
the addition of DTPA [20]. Altematively, it might be that the oxidized DTPA still exhibits
some chelating properties and consequently elirninates the Cu2+ or ~ e ) + induced peracetic acid
decomposition.
2.2 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 7.0
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,
although effect is much greater with the former. It can also be noted that a sharp decrease in
peracetic acid occurs when the reaction time exceeds 20 minutes. Similarly, it was reported
that the addition of DTPA enhances the Fe3+ cataIysed decomposition of hydrogen peroxide
[33]. On the other hand, the addition of DTMPA stabilises hydrogen peroxide, while the
addition of DTPA lads to a much higher consumption rate of hydrogen peroxide relative to
that of the control.
Table 6-2 shows that the DTPA-MnZ' cornpiex is much less stable than the complexes
of DTPA with either ~ e " or Cu", indicating that ~n'+ is not as strongly chelated.
Consequently, 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
weaker DTPA-h4n2+ complex is capable to catalyse peracetic acid decornposition.
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 min of reaction so that their concentrations were the same as those at the start of the
reaction. 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.
Figures 6-6 and 6-7 show the addition of DTPA on the manganese catalysed
decomposition of peracetic acid at pHs of 5.0 and 6.0. 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 6-4,6-6 and 6-7 is also the effect of DTMPA on the manganese
catalysed consumption of peracetic acid. The addition of 0.5 @ DTMPA increases the rate
of peracetic acid decomposition at pHs 6.0 and 7.0 (Figures 6-7 and 6-4). but has a negligible
effect at pH 5.0 (Figure 6-6). Hydrogen peroxide. on the other hand, is stabilised by the
addition of D W A in al1 three cases. Therefore it is proposed that Mn" is oxidized to MnO;
by peracetic acid (Reaction (3)) at pHs 6 and 7 but not at pH 5. Furthemore, hydrogen
peroxide may not be involved in the oxidation and reduction cycle since the oxidation of
DTMPA by MnO,' could be much faster than Reaction (4).
3. 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. First
we performed peracetic acid bleaching of oxygen delignified pulp with and without DTPA
pretreatment. 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
pulp is pretreated with DTPA. By adding manganese (as MnSOJ at a charge corresponding
to the arnount of manganese removed in the chelation stage, 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. We therefore conclude
that manganese present in the unchelated O pulp is mainly responsible for the enhanced
peracetic acid decomposition, and thus causes the less efficient bleaching.
We also studied whether the addition of chelants / additives such as DTPA, DTMPA,
MgSO, or Na,P,O, to the bleaching stage, instead of a pretreatment stage, can effectively
deactivate the metal ions present in pulp fibres (Table 6-3). 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, while the presence of tetrasodium pyrophosphate improves the bleaching
Table 6-3. Peracetic Acid Bleaching of Oxygen Delignified
Sarnple and condition
Unchelated O P U ~ P
Chelated O P U ~ P
Unchelated O pulp, 1.8% Na4P207
added
Unchelated O pulp, 0.3%
DTPA added
--
Unchelated O pulp, 0.3% DTMPA
added
Unchelated O pulp, 0.3%
MgSO.4 added
Softwood Kraft Pulp (O Pulp)
Treatment time (min)
Bright. (%ISO)
3leaching Conditions: 10% consistency, 60°C, lnitial pH of 7.0, 1.5% peracetic acid
Viscosity (mPa-s)
23.4
21.8
23.4
23.0
:harge on 0.d. pulp
47.9 90.2 3 8.5 85.2 26.0 83.7
22.6 9.6 77.2
3.2 5.8 2.9 4.3 2.1 2. I
20.2 O. 1 1.4
8.7 87.3 5.5 83.1 3.7 80.2
22.3 0.2 73.9
21.7 4.8
Residual Chernicals (% on charge)
CH3C03H
- 18.7 10.4 6.0 2.0
- 59.6 5 1.4 35.4 12.3
H20, -
9.1 8.7 7.2 5.1
- 92.5 86.8 83.6 79.8
performance, although not to the level obtained with the chelated pulp. This is in agreement
with the results obtained by McDonough [ZO], who observed that the addition of DTPA
during peracetic acid bleachins of goundwood pulp resulted in a smaller b right ness gain. 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, leading to the
wastefid consumption of peracetic acid without any bleaching effect.
Table 6-3 shows that the residual peracetic acid and hydrogen peroxide concentrations
are lower with the addition of DTPA. As shown in Table 6-1, the oxygen delignified
softwood kraft pulp contains 6 1.5 ppm manganese which corresponds to 6.8 ppm Mn in the
bleaching liquor. Therefore, the manganese induced decomposition of both peracetic acid and
hydrogen peroxide must occur, as was discussed in the previous section. When DTMPA was
added to the peracetic acid bleaching system, the residual peracetic acid concentration was
lower than that of the control experirnent, while the residual hydrogen peroxide concentration
was much higher. These results are similar to those in Figures 6-4 and 6-7 where 0.75 ppm
manganese was added to a peracetic acid solution, suggesting that the same mechanism
prevails in the pulp bleaching systern: i.e. permanganate is fonned from the oxidation of Mn"
by peracetic acid, which then oxidizes DTMPA rather than hydrogen peroxide.
It appears that both the deligiification degree and brightness gain are closely related
to the residual peracetic acid afier bIeaching (Columns 3, 4 and 6). This is not unexpected
since poor bleaching results are obtained when more peracetic acid is consumed in wastefui
reactions. We fùrther tested this hypothesis by comparing the bleaching results obtained with
a constant peracetic acid concentration of 1.679/ L at 40°C and pH 7.0, using both chelated
and unchelated pulps at 1.5% pulp consistency. We found that the delignification degee and
brightness gain were similar. However, much more peracetic acid was required to maintain
the constant peracetic acid concentration for the unchelated pulp.
The decrease in pulp viscosity during peracetic acid bleaching is very small, as shown
in Table 6-3. This is consistent with the generat perception that peroxy acids are selective
bleaching chemicals when used under optimum operating conditions. It appears that the pulp
viscosity a h r Pa treatment is related to the residual hydrogen peroxide present; i.e. 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.
The addition of magnesium suKate has a negiigible effect on the delignification degree
and brightness gain. 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.
Furîhermore, Table 6-3 shows thar the cellulose degradation is not af5ected by the addition
of magnesium suIfàte. These results are not inconsistent with the protective effect of MgSO,
in &O, bleaching and CX_ delignification, since the latter two are performed at a high pH while
a neutrd pH is used for peracetic acid bleaching.
We iùrther studied the effect of different additives on peracetic acid bleaching with
a hemlock kraft pulp, which was first ozone-delignified (see experimental section for details)
followed by an alkaline extraction stage. The results are presented in Table 6-4. 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. This is attributed to
the fact that the transition metal ion content, especially manganese, in the ZnE pulp is much
smaller than that in the O pulp, as was show in Table 6-1. Again, Table 6-4 shows that the
addition of DTPA during peracetic acid bleaching of both the chelated and unchelated pulps
is not beneficial, as evidenced by a lower brightness gain and a higher viscosity loss. Again,
the addition of MgSO, during peracetic acid treatment has a negligible eFect on the bleaching
response.
The results in Table 6-4 were obtained with a peracetic acid charge of 2%. When only
0.5% peracetic acid was charged to the ZnE pulp, the difference with or without DTPA
pretreatrnent was even smaller. 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.
However, a chelation stage as a pretreatment is strongly recommended for peracetic acid
bIeaching of puIp with a high transition metai ion content, especially manganese.
Table 6-4. Peracetic Acid Bleaching of Ozone Deiignified Softwood Kraft Pulp
Sample and conditions
Unchelated ZnE pulp 1 Chelated ZnE pulp 1
Treat Bright. time (%ISO) (min)
-
Viscosity Residual Chernicals (m ~ a - s ) I (% on original)
Unchelated ZnE pulp 0.3% DTPA added in Pa
Unchelated ZnE pulp 0.3% MgSO, added in Pa
Chelated Z n . pulp 0.3% DTPA added in Pa
Bleaching Conditions: 10% consistency, 60°C, Initial pH of 7.0, 2% peracetic acid charge on 0.d. pulp
CONCLUSIONS
The transition metal ion induced decomposition of peracetic acid, and the effect of the
addition of chelantdadditives on the decomposition were studied under typical peracetic acid
pulp bleaching conditions. The results show that a significant amoünt of peracetic acid may
be wasted when metal ions are present, thus resultins in less efficient bleaching. The metal
ion induced decomposition may take place foliowing a radical mechanism. However, an
oxidation-reduction cycle involvinç ~ n ~ ' and MnO; is aiso present when rnanganese is
present in the peracetic acid solution.
It was found that the presence of chelants such as DTPA or DTMPA minimizes the
Cu2' and Fe3+ induced peracetic acid decomposition but increases the Mn" induced
decomposition. This is explained by assuming that the more stable complexes of DTPA or
DTMPA with Cu" and ~ e ) ' do not catalyse the decomposition reactions, while the less stable
DTPA-Mn" complex can, and by the fact that only manganese participates in an oxidation-
reduction cycle, while Cu" and Fe3' do not.
As expected, a close relationship between peracetic acid decomposition and pulp
brightness development was observed and confirmed at constant bleaching conditions. A
chelation pretreatment stage for pulps with a high metai ion content, especially manganese,
lads to improved peracetic acid bleaching. For pulps with a 1ow metal ion content, 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. However,
the addition of some chelants, 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.
ACKNOWLXDGMENT
The author thanks NSERC for financial support in the form of a Strategic Grant and
F. Munro of E. B. Eddy Forest Products LTD for supplying the oxygen delignified softwood
krafl puIp.
RIEFERENCES
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Springer, E. L., Delignification of Aspen Wood using Hydrogen Peroxide and Peroxyrnonosulfate ,Tappi J., 73( 1 ): 175 (1 990)
Hili, R T., P. B. Walsh and J. A. Hollie, Peracetic Acid, an Effective Alternative for Chlorine Compound Free Delignification of Kr& Pulp, TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 12 19.
Bailey, C.W. and C.W. Dence, Peroxyacetic Acid Bleaching of Chemical Pulp, Tappi J., 49(1):9 (1966)
Devenyns, J., F. Desprez and N. Troughton, Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion corn Conventional Chlorine Bleaching via ECF toTCF, TAPPI 1993 Pulping Conkence Proceedings, TAPPI PRESS, Atlanta p. 341.
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 1996 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., HHI, SC, March, 1993
Troughton, N., F. Desprez and J. Devenyns, Peracids: The Pathway to High Brightness TCF Kraft Pulps, Proceedings of 1994 International Pulp Bleaching Conf , Vancouver, June, 1994
Amini, B. and J. Webster, On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule, and Considerations on How to Select Among Them, 1994 TAPPI Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 37 1.
Liebergott, N., Peracid Delignification and BIeaching of Chemical Pulp Part II: Oxidation, Pulp & Paper Canada, 97(3):73 (1996)
Devenyns, J., F. Desprez, N. Troughton, and L. Plumet, MetaIs Control in TCF Bleaching - Implications for Kraft Bleaching Sequence Design, 1994 TAPPI Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p.3 8 1.
Chirat, C.and D. Lachenal, Benificid and Adverse Effect of Meta1 Ions in ZP Bleaching Sequences, 1994 TAPPI Pulping Conference Proceedings, TAPPI PRESS,
Atlanta, p. 1239
Lapierre, L., J. Bouchard, R. M. Berry, and B. van Lierop, Chelation Prior to Hydrogen Peroxide Bleaching of Kraft Pulps: an merview, Preprints, 8 1 st CPPA annuai meeting, Montreal, Jan., 1995, pl3233
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):T20 1, 1965
Jayarnant, M. D. and E. J. DeGraw, Practical Implications of Met& Management in Totdy Chlotine-Free (TCF) Pulp Production, Proceedings of 1 994 International Pulp Bleaching Conf, Vancouver, June 1994
Gierer, J., K. Jansbo, E. Yang, B.H. Yoon, and T. Reitberger, On the Participitation of Hydroxyl Radicals in Oxygen and Hydrogen Peroxide Bleaching Process, Procdmgs 6th Int. Symp. On Wood and Pulping Chernistry, Melbourne, Australia, Vol. 1, p.93 (199 1)
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Koubek, E., The Kinetics and the Mechanisrn of the Decomposition of Aiiphatic Peroxyacids in Aqueous Solutions, Ph.D thesis, Brown Univ. , 1964
Vasyutyn, Ya. M., V. O. Gavenko and 1. A. Garbuzyuk, Influence of Minera1 Salts on the Decay Rate of Peroxyacetic Acid in Aqueous Solution, Ukrainskii Khirnicheskic Zhumal, 55(6):584 (1 989)
Allen, G.C. and A. Aguilo, Metal Ion Catalysed Oxidation of Acetaldehyde, Advances in Chemistry Series, 76, p.363 (1 968)
McDonough, T. J. M., Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Alkaline Solutions, Ph.D Thesis, University of Toronto (1972)
Swem, D., Ed., Organic Peroxides, Vol.1, John Wiley and Sons, N. Y., 1970 , p.362
Gang, K. J., Y. Ni and A.R.P. van Heiningen, Mechanism of Cellulose Protection in a Novel and Selective Ozone Pulp Bleaching Process, Preprints, 82nd CPPA Annual Meeting, Montreal, Jan., 1996, p. B303
Greenspan, F.P. and D. G. Mackellar, Analysis of Aliphatic Peracids, Analy. Chem., 20(11):1061 (1948)
Evans, D. F. and M. W. Upton, Studies on Sin~let Oxygen in Aqueous Solution, Part 3, J. Chem. Soc. , Dalton Trans., 1985, p. 1 15 1
Kagan M. J. and G. D. Lubarslq, The Intermediate Stages of Aldehyde Oxidation, J. Phys. Chem., 39, 837-847 (1935)
van Lierop, B., N. Liebergott and M. G. Faubert, Using Oxygen and Peroxide to Bleach Kr& Pulps, Preprints. 79th CPPA Annual Meeting, Montreal, 1993, p.B2 1
Allison, R. W., Peroxide Bleaching of Mechanical Pulp fiom Pinus Radiata, Appita, 36(5):362 (1 983)
Solines, M., Brightening Response of Western Hemlock Refiner Groundwood to Hydrogen Peroxide, Pulp Paper Can., 77(3):59 (1 976)
Anderson, R, E. Stenberg and B. Sjogren, Optimised Hydrogen Peroxide Bleaching in Closed White-water Systems, Tappi J., 63(4): 1 1 l(1980)
Rapson, W. H., M. Wayman and C. B. Anderson, Hydrosulphite and Peroxide Bleaching of Nine Pure Species Groundwoods, Tappi J., 48(2): 1 13 (1 965)
Thiessn, F. I., Finlay Forest Uses Flash Dryer as Reaction Tower for Bleaching Pulp, Pulp & Paper, SS(1): l6l(l979)
The Dow Chernical Company, Versene Chelating Agent, Midland, Michigan, p 4.12 (1 993)
Colodette, J. L., S. Rothenberg and C.W. Dence, Factors Mecting Hydrogen Peroxide Stabiiity in the Brightening of Mechanical and Chernimechanical Pulps. Part III: Hydrogen Peroxide Stability in the Presence of Magnesium and Combinations of Stabilizers, JPPS, 1 5(2): 545 ( 1989)
0.07 -i-CH,C03H, 0.5 S/L DTMPA -0- H,O,, 0.5 S/L DTMPA z : -A-CH,CO,H, C~(l1) -A- H20, C~( l l )
0 10 20 30 40 50 60
Time (min)
Figure 6-1. Effect of transition metal ions on the stability of a peracetic acid solution (40°C, pH 7,0,0.75 ppm metal ion concentration)
-a-CH,CO,H, Control -d- H20,, Control J : -HH,CO,H, Na4P20, + H,02, Na4P20,
E "O6 - . <H,CO,H, DTPA -O- H,O,, DTPA
w -mUH,CO,H, OTMPA -n- H,02, DTMPA c &H3C03H, MgSO, 4 H202, MgSO, .O 0.05 c. e u c 8 0.04 C
O 0; 043 I L
O 0.02 =, O 3 0.01 O
0.00 O 10 20 30 40 50 60
Tirne (min)
Figure 6-2. Effect of additives on copper catalysed peracetic acid decomposition (40°C, pH 7.0,0.75 ppm Cuz+, 0.5 g L DTPA, DTMPA or MgSO,, 2 g/L Na,P,O,)
O 10
Time (min)
0.07
Figure 63. Effect of additives on iron catalysed peracetic acid decomposition (40°C, pH 7.0,0.75 ppm Fe*, 0.5 0.5 DTPA, DTMPA or MgSO,, 2 g/L Na,P,O,)
î 5 E 0."- w
s n ---
-A- CH,CO,H, Control -A- H202, Control - CH,C03H, Na4P20, -o- H202, Na4P,0, - - CH3C03H, DTPA -O- H202, DTPA -i-CH3C03H,DTMPA -0-H,O,,DTMPA + CH,CO,H. MaSO. + H-O-. MaSO-
I --
A -A4H,CO3H, Control -A- H202. Cont rol - H H 3 C 0 3 H , Na,P20, -XP- H202, Na4P207 --4H,C03H, DTPA + H,O,, DTPA -i-CH,C03H, DTMPA -0- H~O; DTMPA ,H3C03H, MgSO, -O- H20,, MgSO,
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 Mn2', 0.5 g/L DTPA, DTMPA or MgSO,, 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 7.0,0.75 ppm Mn2+, 0.5 g/L DTPA )
-A- CH,CO,H, Control -A- H20,, Control -r- CH,CO,H, DTMPA -D- H20,, DTMPA -0- CH,CO,H, DTPA -O- H,02, DTPA
-13 O O
+-L* --O -
0 1-0 20 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)
Time (min)
Figure 6-7. Effect of DTPA or DTMPA on the manganese catalysed decomposition of peracetic acid (40°C, pH 6.0,0.75 ppm ~ n " , 0.5 g/L DTPA or DTMPA)
CHAPTER 7
THE FORMATION OF GASEOUS PRODUCTS AND ITS RELATION TO PULP
BLEACHING DURING THE PERACETIC ACID TREATMENT
When used in pulp bleaching, peracetic acid is consumed by two cornpetitive
pathways: oxidation of pulp and wasteful reactions such as decomposition and combination
with peroxide. In this chapter, the peracetic acid consumed in wastefbl reactions is quantified
by determining the gaseous products evolved. It is found that aithough carbon dioxide is
formed under certain conditions, oxygen is the dominant product of the wastefül reactions.
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. Therefore, the brightening efficiency during peracetic acid treatment
can be determined by measuring the oxygen formation. The peracetic acid brightening results
for an oxygen delignified s o ~ o o d kraft pulp are reported. It is found that a significant
amount of peracetic acid is consumed by the wastehl reactions during the brightening. The
effect of process parameters on the peracetic acid brightening efficiency is determined. 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. This suggests that the oxygen formation can be
used for control of an industrial peracetic acid treatment.
Keywords: peracetic acid, bn~htening, decomposition, gas formation, oxygen delignified softwood kraft pulp
INTRODUCTION
Peracids, 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. Under typical peracetic acid bleaching conditions, in addition to the desirable
Iignin oxidation reactions, peracetic acid may be consumed by spontaneous and transition
metal catalysed decomposition reactions [9- 141. Therefore, it is important to understand and
monitor the peracetic acid decomposition in order to minimize these wastefùl side reactions
during peracetic acid bleaching.
Martin [ I 51 and later Gonzalez-Siena [ 1 61 studied hydrogen peroxide decomposition
by monitoring the gas formation dunng peroxide bleaching of groundwood pulps. It was
found that oxygen is the only gas formed from hydrogen peroxide decomposition, and that
two moles of hydrogen peroxide are decomposed per mole of oxygen formed. It was also
established [Io] that under typical hydrogen peroxide bleaching conditions the oxygen
produced does not contribute to pulp bteaching.
Gaseous products are also formed during peracetic acid decomposition [ 1 O- 131.
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. Later, 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. 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. However, it was found by Koubek [13] who studied the
cobalt catalysed decomposition of peracetic acid at pH 5.4 in an ammonium acetate buffer,
that both oxygen and carbon dioxide were formed in a ratio of about one to one.
Furthemore, Koubek [ 131 also established that roughly 80% of the carbon dioxide formed
originated fiom the acetate ion of the buffer.
The above authors did not extend their studies to a neutd pH range, which is optimd
for peracetic acid brightening [1,8,9,17]. Furthermore, the relationship between the gas
formation and efficiency of peracetic acid brightening has never been exarnined. In this
chapter, the relationship between gas formation and peracetic acid consumption is determined
for typical peracetic acid brightening conditions. Subsequently it is attempted to relate the gas
formation to the brightening efficiency during peracetic acid treatment of an oxygen
deIignified softwood kraft pulp.
EXPERIMENTAL
Peracetic acid and ultra-pure grade NaOH were purchased ftom Aldrich (Milwaukee,
USA). The peracetic acid consists of about 34% w/w peracetic acid, 5% wlw hydrogen
peroxide and 4û% w/w acetic acid with the remainder being water. Reagent grade chemicals,
DTPA fiom Fisher Scientific (Nepean, Ontario) and DTMPA from Buckman (Memphis,
USA) were used in the experiments without hrther purification. Distilled and deionized
water was used in ail experiments. Its metal ion content was below the detection limits of the
atomic absorption (AA) spectroscopic analysis method used in this study.
The oxygen delignified softwood kraft pulp used for peracetic acid bleaching had a
37.7% ISO brightness, a kappa number of 13.8 and a viscosity of 23.4 mPa-S. The chelation
stage (Q) with 0.5% DTPA was performed at SOT, pH 5 , 2.5% pulp consistency and 30
minutes.
The experimental setup was s h o w in Figure 7-1. Experiments without pulp fibres
were carried out in a well sealed 500 mL four-neck round-bottom flask immersed in a
constant temperature bath. The aqueous solution containing al1 the required chernicals except
peracetic acid was preheated to the desired reaction temperature. The reaction was initiated
by addition of a concentrated peracetic acid solution to the reaction flask. The pH was kept
constant with an automatic titrator by addition of 10 m o n NaOH. Mixing was provided by
a submersed 41 mm long magnetic stirrer bar driven by a magnetic drive placed undemeath
the constant temperature bath. 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 ). Any leaks of the system can be
detected by the appearance of nitrogen in the gas sarnple. The gas partitioner employs a dual-
column, dual-detector chrornatographic system to separate and measure the gaseous
products. The first column is packed with 80-100 rnesh Columpakm PQ and the second with
60-80 mesh Molmlar Sieve 13X. The flow rate of the helium transport gas was controlled
by a mass flow controller (Edwards Model 825). The gas in the sampling loop was injected
at predetermined time intervals into the gas partitioner for analysis. SampIes of peracetic acid
solution were also withdrawn with a syringe, weighted and analysed following the iodometric
method developed by Greenspan and Mackellar [ l 81.
The volume concentrations of oxygen and carbon dioxide in the helium gas Stream are
related to the different gas flow rates as:
where F(O3 and F(C0J represent the volumetric flow rates of oxygen and carbon dioxide
respectivefy generated by the reaction solution, and F(He) is the helium fi ow rate. By solving
Equations (1) and (2), one can calculate F(O3 and F(C02) as:
By integrating
WJ = W e ) . [O,]
1 O0 - [O2] - [CO,]
the flowrates of 0, and CO, fiom time t, to t, the volume of 0, and CO,
evolved during t i i e intemal of t, to t, can be determined. The volume of 0, and CO, evolved
was then converted into moies using the ideal gas faw. 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, and t,.
Peracetic acid brightening of pulp was conducted in a 1000 mL four-neck round
bottom flask at 0.5 and 1.5 % consistency, with mixing provided during the course of
brightening by a mechanical stirrer. Again ultra pure helium was bubbled through the
suspension to cany the gaseous products out of the reaction. However, now al1 the gas was
collected in a I O L Tedlar gas sampiing bag. The helium gas flow rate was kept around 50
mL/min with the mass flow controller. The total gas volume collected was measured by
water displacement and the gas composition was determined by anaIysis with the gas
partitioner. After the peracetic acid treatment, the pulp was thoroughiy washed with deionized
water and made into handsheets. Samples of the spent liquor were withdrawn and titrated
for the residual peracetic acid and hydrogen peroxide concentrations.
Pulp brightness, viscosity and kappa number were determined in accordance with
TAPPI methods T452 om-92, T230 om-89, and T236 cm-85, respectively.
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 8.2 and 25°C
with 0.5 g/L DTMPA present was presented in Figure 7-2. The flow rate of helium was 100
mL/min and the mixing speed was 400 rpm. It was established in Chapter 4 that the
disappearance of peracetic acid under this condition is mainly due to the spontaneous
decomposition, as iliustrated in Equation (5):
2 CH3C0,H -+ 2 CH,CO,H + 0, (5)
Figure 7-2b shows that a negligible amount of CO, is released and that O, is the only
ças generated in the system at this condition. The experiments were repeated at helium
flowrates of 70 and 300 &min, and stimng speeds of 200 and 800 rpm. It was found that
the oxygen formation is not af5ected by the helium gas flowrate or the mixing speed. This
means that there are no significant transport limitations for the release of oxygen from the
reaction system.
By plottins the peracetic acid consumption against the oxygen formation in Figure 7-
3, 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 (5). Similar experiments at pH of 7.0 and 6.0 under
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.
It was found [ 10- 13,191 that trace amounts of transition metal ions, such as cobalt,
manganese, copper and iron catalyse the decomposition of peracetic acid. Among these
metals, manganese is the main catalytic species responsible for enhanced peracetic acid
decomposition during pulp bleaching as shown in Chapter 6. Therefore, 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 0.75 ppm Mn(I1)
without the addition of DTMPA at pH 8.2 and 25°C (Figure 7-4). As expected, the presence
of Mn(I1) enhanced the disappearance rates of both peracetic acid and hydrogen peroxide
(Figure 7-4a). Similady, the 0 formation was also increased with the addition of Mn(Il), but
the amount of CO, released was still negligible (Figure 74b). 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.
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. The overall reaction was
reported as [20]:
Furthermore, it was established in Chapter 6 that there is also an oxidation-reduction cycle
in the reaction system with the addition of Mn" . The overall stoichiometry of the oxidation-
reduction cycle is the same as Reaction (7). As is evident fiom Reactions (5), (6) and (7),
the molar ratio of the consumption of oxidants and the formation of oxygen is always 2
consistent with the experimental evidence.
The effect of pH on the formation of gaseous products in the presence of 0.75 ppm
Mn" was firther investigated by decreasing the pH eom 8.2 to 5.0. As shown in Figure 7 3 %
the disappearance rates of both peracetic acid and hydrogen peroxide are much slower at pH
5.0 than at pH 8.2. This is due to the fact that the reaction rates of Reactions (9, (6) and (7)
are al1 decreased at a Iower pH, as discussed in Chapter 5 . Figure 7-5b shows that both
oxygen and carbon dioxide are generated at pH 5.0. Further experiments showed that the
formation of COz is increased by the addition of acetic acid in the presence of ~ n ' + . This is
in agreement with the earIier result by Kagan and Lubarsky [ 1 0 3 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. In addition,
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 5.4. As will be shown below, the present experimental evidence as well as that
reported in literature support that carbon dioxide is the fkrther oxidation product of acetic
acid, rather than a direct product fiom the decomposition of peracetic acid.
In the previous section it was shown that two moles of the oxidants, peracetic acid
and hydrogen peroxide, are consumed per mole of oxysen generated. Therefore for the
experiments at pH 5.0 described above, the amount of oxidant consumed was corrected for
the oxygen formation according to the stoichiometry of Reactions (S), (6) and (7).
Subsequently the molar carbon dioxide formation was plotted against this corrected rnolar
amount of oxidant consumed. As can be seen in Figure 7-6, the stoichiometry in terms of
moles of corrected percetic acid and hydrogen peroxjde consumed per mole of carbon dioxide
formed is approximately 3. 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.
Therefore, the mechanism in Figure 7-7 is proposed to account for the formation of carbon
dioxide. The singlet oxygen, formed in Reactions (S) , (6) and (7) oxidizes acetic acid to
produce a-peroxide compound O), which undergoes decarboxyiation under acidic conditions,
generating d o n dioxide and fomaldehyde. Subsequently. fomaldehyde is further oxidized
by peracetic acid to formic acid as identified experimentally by Kagan and Lubarsky [IO].
Thus, the proposed mechanism satisfactorily accounts for the observed stoichiometry of the
oxidant consumption and the carbon dioxide formation. In addition, it explains why a lower
pH favours the formation of carbon dioxide.
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 8.2 was examined by adding either DTPA or DTMPA at the mid
point ofthe reaction (at 30 minutes). As s h o w in Figures 7-8 and 7-9 respectively, there is
a sharp increase in peracetic acid consumption rate when 0.02 mol/L DTPA was added with
or without the addition of 0.75 ppm Mn(I1) (Figure 7-8a). 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]. 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. 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. It is also shown in Figures 7-8a and 7-8b that the addition of 0.02 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. 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 [ 1 41.
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. 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]. Furthemore,
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 Formation of Gaseous Products and Its Relation to Peracetic Acid Bleaching
The effect of chelation, pH, pulp consistency, peracetic acid charge and reaction time
on the gas formaion and its relation to pulp brightening during peracetic acid treatment were
studied. The results of the peracetic acid treatment of an oxygen delignified pulp are
presented in Table 7-1. Listed are the development of the residuaI amount of peracetic acid
and hydrogen peroxide, the amount of Oz and CO1 formed, and the bnghtness and viscosity
of the bleached pulp. The amount of peracetic acid and hydrogen peroxide consumed in
wastefiil reactions is calculated fiom the formation of O2 and CO2 using the appropriate
stoichiometry. Since it is reasonable to assume that at the present conditions hydrogen
peroxide is ody consumed in wastehl reactions, i.e. does not contribute to pulp oxidation,
the amount of peracetic acid consumed in wastefùl reactions can be calculated fiom the gas
fornation results and the amount of hydrogen peroxide consumed. Subsequent Iy 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. Both the development of peracetic acid consumed in pulp oxidation reactions and
that in wastefbl reactions are given in Table 7-1 expressecl in tems of percentage on 0.d. pulp
as well as of percentage of total arnount of peracetic acid consumed. The results in Table 7- 1
show that only oxygen is produced when peracetic acid brightening is performed at pH 7.
However, at pH 5 (Run 5) a small amount of carbon dioxide is formed. 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. These results are consistent with those obtained at the same conditions
Table 7-1. The formation of gaseous products and its relation to bleaching during peracetic acid treatment of an oxygen delignified pulp
(Initial brightness of 37.7
1 Experimental Runs 1
6ISO; initial
II Samples
h l p consistency (%)
Pa Charge (% on 0.d. pulp)
II Temperature (OC) 1 60
Bleaching tirne (min) 120
Residual Pa 1 O-O9
Il Residual H202 (% on 0.d. pulp)
O formation
CO, formation (mmol CO, / g Pa charged)
II Viscosity (rn~a .~) 1 20.6
II Pa consumed in pulp oxidation (% on 0.d. pulp) 1
II I Pa consumed in wastefùl 2.36 reactions (% on 0.d. pulp)
II H,02 consurned in wastefid 0.43 reactions (% on 0.d. pu~p) I
Pa decomposed 81
TotaI Pa consumed (%)
Pa consumed by oxidation Total Pa consumed (%) 1 l9
* pH was kept constant dunng the blëaching
but without the presence of pulp fibres, presented in the previous sections. A surpnsing result
ofthe analysis in Table 7-1 is that the majority of the peracetic acid is consumed in wastehl
reactions, accounting for 59 to 87% of the total peracetic acid consumed. The amount of
peracetic acid wasted was plotted against the hydrogen peroxide wasted for al1 the
experiments listed in Table 7-1. Figure 7-10 shows that the molar ratio of peracetic acid
wasted and hydrogen peroxide wasted is about 2. Since hydrogen peroxide is only wasted in
Reaction (7) with a molar ratio of 1 between peracetic acid and hydrogen peroxide 1141,
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.
Cornparison of Run 1 with Run 2 confirrns that DTPA pretreatment leads to Iess
peracetic acid decomposition and a higher brightness gain, obviously because the DTPA
chelated pulp contains less residuai transition metals as shown in Chapter 6. The effect of pH
on peracetic acid brightening is seen by comparing Run 5 and 2 at pH 5.0 and 7.0
respectively. The analysis shows that a higher pH leads to more oxidation of pulp and
subsequently a higher brightness gain. This is consistent with literature results [ 1,8,9,, 171 that
peracetic acid brightening is more effective at a neutral pH than at a sliçhtly acidic condition.
However, 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. An important result is that the data in Table 7- 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). Therefore a higher brightness gain and especially a higher brightening
efficiency can be expected when peracetic acid brishtening is performed at hiçh consistency.
As expected a h i ~ e r brightness sain is obtained at higher peracetic acid charse under
otherwise the same brightening conditions (see Runs 8, 2 and 3). However, an increase in
peracetic acid charge results in a siçnificant lower briçhteninç efficiency. This could be
explaùied by the fact that at a higher Pa charge the reactive lignin chromophores are rapidly
consumed, while the peracetic acid concentration is still hi& so that the wastefûl reactions
remain substantial. 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).
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. Figure 7-1 1 shows that there is a unique relationship between these two parameters,
independent of the process conditions. This confirms that the peracetic acid consumption in
wastefil reactions and by pulp oxidation are two completeiy independent phenornena,
therefore, the practical importance of Figure 7- 1 1 is that the bnghtness gain and brightening
efficiency can be predicted for a particular pulp independent of the process conditions, Frorn
the peracetic acid consumption (Le. charçe minus residual) and the gas (O2 and CO2 )
generation. This constitutes a powefil tool for control and optimization of an industrial
peracetic acid stage.
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; a higher Ioss of hydrogen
peroxide in wastefiil reactions is always accompanied by a lower pulp viscosity. This may be
explained by the hct that highly reactive oxyçen species, such as singlet oxyçen and radicals,
are generated in the wasteful reactions involved hydrogen peroxide. This is in agreement with
the findig by Devenyns et ai. [21] that distilled peracetic acid (almost no hydrogen peroxide)
is more selective than equifibnum peracetic acid in pulp delignification. Since Figure 7- 10
shows that hydrogen peroxide and peracetic acid consumed in wastefùl reactions is closely
related, 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. Figure 7- 12b shows that this
is indeed the case. The practical implication of Figure 7- 12b is that the pulp viscosity after
peracetic acid treatment can also be predicted for a particular pulp independent of the process
conditions, fiom the measurement of gas generation.
CONCLUSIONS
Oxygen is the main gaseous product produced fiom the decomposition of peracetic
acid under typical brightening conditions, i.e. pH 7 and 60°C. One mole of oxygen is
generated per two moles of oxidants (peracetic acid and hydrogen peroxide) consumed. At
a relatively low pH (-5) CO, may also be formed fiom the wasteful reactions at a
stoichiometry of 3 moles of oxidant consumed per mole of COS released. Thus, 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. Furthemore, 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. charge minus residual) and that what is
wasted.
It is found that the pulp brightness gain is directly reiated to the peracetic acid
consumption in the oxidation of pulp, independent of the process conditions. 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, and CO, çeneration.
Similady, the pulp viscosity loss is uniquely related to the loss in oxidant as measured by the
O2 and C O generation. These findings constitute a powerfùl tool for control and optirnization
of an industriai peracetic acid stage.
ACKNOWLEDGMENT
The author thanks NSERC for financial support in the forrn of a Strategic Grant and
F. Munro of E. B. Eddy Forest Products LTD for supplying the oxygen delignified softwood
kraft pulp.
REFERENCES
Bailey, C. W. and C. W. Dence, Peroxyacetic Acid Bleaching of Chemical Pulp, Tappi J., 49(1):9 (1966)
Hill, R. T., P. B. Walsh and J. A. Hollie, Peracetic Acid, an Effective Alternative for Chlorine Compound Free Ddjgnjfication of Kr& Pulp, TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Boston, p. 12 19.
Springer, E. L. and J. D. McSweeny, Treatment of Softwood Kr& Pulps with PeroxymonosuIfate Pnor to Oxygen Delignification, Tappi J . , 76(8): 1 94 (1 993)
Geng, 2. P., H-m. Chang, H. Jarneel, B. Evans, B. Amini, and J. R. Webster, Mixed Peracids: Manufacture and Use as Non-Chlorine Delignification and Bleaching Agents, 1993 TAPPI Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p.353.
Troughton, N., F. Desprez and J. Devenyns, Peracids: The Pathway to High Brightness TCF Kraft Pulps, Proceedings of 1994 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Amelia Island, FL, sec. 10- 1.
Amini, B. and J. Webster, On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule, and Considerations on How to Select Among Them, 1994 TAPPI Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 371.
Allison, R. W. and K. G. McGrounther, Improved Oxygen Delignification With Interstage PeroxymonosulfÙnc Acid Treatment. Tappi J., 78(10): 134 (1 995)
Liebergott, N., Peracid Delignification and Bleaching, 1994 TAPPI Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 357.
Yuan, Z., Y. Ni and A-RP. van Heiningen, Kinetics of Peracetic Acid Decomposition, Part 1 and Part II, Canadian Journal of Chemical Engineering, 75,37-47 (1 997)
Kagan, M.J. and G. D Lubarsky. The Intermediate Stages of Aldehyde Oxidation, J. Phys. Chem., 39, p.837 (1935).
Allen, G. C. and A. Aguilo, Metal ion catalyseci oxidation of acetaldehyde, Advances in Chemistry Series, 76, p.363 (1 968).
Vrbaski, T. and 1. Brihta The Kinetics of Oxidation of Ndehydes to Acids and Acid
Anhydrides, Arhiv Za Kemiju, 26, p.267 ( 1954).
Koubek, E., The Kinetics and the Mechanism of the Decornposition of Aliphatic Peroxyacids in Aqueous Solutions, Ph.D thesis, Brown Univ. , 1964. Martin, D. M., The Bleachinç of Eastern Spruce Groundwood with Alkaline Peroxide 1. Reaction Kinetics, Tappi J., 40(2):65 (1 957)
McDonough, T. J. M., Peracetic Acid Decomposition and Oxidation of Lignin Model PhenoIs in Alkaline Solutions, Ph.D Thesis, University of Toronto (1 972)
Martin, D. M., The Bleaching of Eastern Spruce Groundwood with Alkaline Peroxide 1. Reaction Kinetics, Tappi J., 40(2):65 (1957)
Gonzalez-Sierra, G., The Effect of Process Variables on the Decomposition of Hydrogen Peroxide in the Bleaching of Groundwood Pulp, MSc. thesis, State Univ. Of New York, College of Environmental Science & Forestry, Syracuse, N.Y., (1 977)
Rapson, W. H., The RoIe of pH in Bleaching, Tappi J., 39(5):284 (1956).
Greenspan, F. P. and D. G. Mackellar, Analysis of Aliphatic Peracids, Analy. Chem., 20(11): 1 O6 1 (1 948).
Vasyutyn, Ya. M., V. O. Gavenko and 1. A. Garbuzyuk, lnfluence of mineral salts on the decay rate of peroxyacetic acid in aqueous solution, Ukrainskii Khimicheskic Zhumal, 55(6):584 (1 989)
Evans, D. F. and M. W. Upton, Studies on Singlet Oxygen in Aqueous Solution, Part 3, J. Chem. Soc., Dalton Trans., p. 1 15 1, 1985
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 hlps, Proceedings of 1993 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., HHI, SC, sec. 8- 1
f'7- Mass Flowmeter
Auto Reaction Titrator Vessel in
Bath
u 2-way Swagelok s O Whitey Valve 1, 2 Calibration Gases
Figure 7-1. The experimentrl setup for the determiiiation of grseous products during peracetic rcid decomposition
5 3 O 15
O, Formation (mmol)
Figure 7-3. The stoichiometry of the peracetic acid consumption and the oxygen formation at 25*C, pH 8.2, F(He) of 100 mL/min and with 0.5 g/L DTMPA addition
2 4 6
CO, Formation (mmol)
Figure 7-6. The stoichiometry of peracetic acid consumption and carbon dioxide formation in the presence of 0.75 ppm Mn(ïï) and at 25OC, p H 5.0, F(He) of 100 mllm in)
1 I I "T-\ oz*
H O-H -
Figure 7-7, Plausible mechanism of the carbon dioxide formation during peracetic acid decomposition
Time (min)
(a)
O 20 40 60 80
Time (min)
(b)
Figure 7-8. The effect of DTPA addition on peracetic acid consumption and the oxygen formation nt 25OC, pH 8.2, F(He) of 100 mllmin and with 0.02 niol/L DTPA added at 30 min
O 1 2 3 4 5 6 7 8
H,O, wasted (mmol)
Figure 7-10. The relationship between the wasted peracetic acid and hydrogen peroxide (O or OQ pulp, 40-60°C, pH 5-7, 1.5-596 peracetic acid charge, 0.5-1.5% pulp consistency, 30-120 min)
CH,CO,H consurnption in pulp oxidation (% on 0.d. pulp)
Figure 7-11. The relationship between the peracetic acid consumption due to the pulp oxidation and the pulp brightness (O or OQ pulp, 40-6O0C, pH 57, 1.55% peracetic acid charge, 0.5-1.5% pulp consistency, 30-120 min)
0.0 0.2 0.4 0.6 0.8 1 .O
H202 wasted (% on 0.d. pulp)
(a)
O 2 4 6
CH3C03H and H,02 wasted (% on 0.d. pulp)
(b)
Figure 7-12. The relationship between the pulp viscosity and the oxidant coiisunied in wasteful reactions (O or OQ pulp, 40-60°C, pH 5-7,1.5-5% peracetic ricid charge, 0.5-1.5% pulp consistency, 30-120 min)
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. The model consists of three paralle1 and one consecutive reaction, and
is based on reaction pathways reported for lignin model compounds with peracetic acid. An
optimization search aigorithm 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.
Keywards: Peracetic acid brightening, kinetic model, chromophore, light absorption
coefficient, ozone deIignified softwood kraft pulp
INTRODUCTION
Peracids have recently emersed as a potential alternative to chlorine containing
chemicais for bleaching of chemid pulps [ I - 131. It has been shown [l -2,13- 1 71 that peracetic
acid is a good delignifier when used in the prebleaching s tqes . In addition, peracetic acid (Pa)
can also be applied in the Iater brightening stages as a substitute for chIorine dioxide [2,8- 1 O].
As shown in Chapter 3, 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 which Zn represents a solvent-assisted ozone stage. For example, it was reported in
Chapter 3 that a ZnEo delignified Hedock kraft pulp with a bnghtness of 56.5% and
viscosity of 28.4 mPa.s is bIeached by the Pa stage to a brightness of 82.7% while maintaining
a viscosity of 26.6 mPas with only about 1.5% peracetic acid by weight as peracetic acid, or
0.66% as hydrogen peroxide. In the present chapter, a kinetic model is developed for the
peracetic acid bnghtening of a methanol-assisted ozone delignified and subsequently alkaline
extracted (i-e. ZnE) pulp.
The constant condition method of kinetic experimentation in which the bleaching
chemicai concentrations, pH and temperature are held constant during the course of reaction
was used in the present study . The kinetic data was obtained by following the light absorption
coefficient of the bleached pulp. 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 [23,24].
The kinetic model presented in this chapter consists of three parallel reactions and one
consecutive reaction, al1 representing reaction pathways identified in lignin mode1 cornpound
studies with peracetic acid. First order reaction behaviour with respect to the chromophore
and peracetic acid (or peracetate anion) concentrations were assumed. This approach is
different fiom that of other studies [IS-20, 23,241 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 initial values were
estimated fiom the data at conditions when only one or two reactions dominated the
brightening development.
EXPERIMENTAL
Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fi-om Aldrich
(Milwaukee, USA). The equiiibnum peracetic acid consists of about 34% wlw peracetic acid,
5% W/W hydrogen peroxide and 40% wlw acetic acid with the rernainder being water.
Distilled and deionized water was used in al1 experiments. Its metal ion content was below
the detection limits of the atomic absorption (AA) spectroscopic anaIysis method used in this
study.
An ozonated and alkaline extracted softwood kraft pulp of 2.8 1 m'/kg absorption
coefficient, 47.5% ISO brightness, 6.7 kappa number and 27.1 mPa-s viscosity was used in
this study. Ozone bleaching (Zn) was carried out on a Hernlock kraft pulp impregnated with
70% methanol-water of pH 2, following an earlier descnbed procedure 1261. The ozone
charse was 1.60/0 @y weight on 0.d. pulp) of which 90% was consumed. A subsequent alkali
extraction stage (E) was perforrned at pH 1 1 .O, 77"C, IO% pulp consistency for 45 minutes.
The peracetic acid bleaching experiments at constant peracetic acid concentration
were canied out in a 1000 mL four-neck, well stirred, round-bottom flask immersed in a
constant temperature bath. 3 g r a m o.ci. pulp was used in each experiment and the pulp
consistency was 0.3%. The pulp s l u q was preheated to the desired temperature. A suitabie
amount of NaOH was then added to adjust pH to the desired level. Subsequently, the
required amount of peracetic acid solution was added to initiate the bleaching. The pH was
kept constant with an automatic titrator by addition of 10 m o n NaOH. Preliminary bleaching
nins were conducted to determine the rate of peracetic acid consumption. Subsequently, the
desired amount of peracetic acid was charged to the reaction mixture at regular time intervals
to maintain a constant peracetic acid concentration. The maximum change in peracetic acid
concentration was les than 10%. The bleaching reaction was quenched by injecting an excess
amount of KI dissolved in dilute sulfiiric acid. The pulp was immediately washed with
deionized water, and two hand sheets were made according to Tappi standard method T272
orn-92.
The peracetic acid and hydrosen peroxide concentrations were determined foltowing
the iodometric method developed by Greenspan and Mackellar [27]. The absorption
coefficient was determined at 557 nm wavelength with Technjbrite Micro TB- 1 C. The pulp
bnghtness was determined following TAPPI method T452 0111-92. The viscosity and kappa
number were deterrnined in accordance with T330 om-89 and T236 cm-85 respectively.
RESULTS AND DISCUSSION
Since the light absorption coefficient of pulp is directly proportional to its
chromophore concentration, the kinetics of peracetic acid brightening are described in tenns
of the rate change in the light absorption coefficient. Figure 8-1 shows the results obtained
at different pHs but a constant peracetic acid concentration of 0.0493 mol/L and temperature
of 50°C . It is evident that the light absorption coefficient decreases rapidly at the beginning,
but that the decrease becomes increasingly slower as the reaction continues. A similar
behaviour has been observed for chlorine dioxide bleaching of chemical pulps and hydrogen
peroxide bleaching of mechanical pulps [18-241. As in these two other cases, this pattern
could be explaineci by large differences in reactivity of the different chromophore structures.
It is noted that pH has a significant eEect on both the chromophore disappearance rate
and the final degree of chromophore removal. When the pH increases fiom 1 to 7, both of the
above two parameters increase. However, as the pH increases hrther fiom 7 to 10, the initial
chromophore disappearance rate is unchanged while the final degree of chromophore
rernoval is reduced. These results are consistent with the general knowledge t hat the optimum
pH of a peracetic acid brightening stage is in the neutral range [8,14,28].
The development of the light absorption coefficient at pH 6.0 and different peracetic
acid concentrations varying fiom 0.0329 to 0.0658 moi/L was also determined. 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. The results
listed in Table 8-1 as well as those in Figure 8- 1 forrn the data base for the determination of
the kinetic parameters during peracetic acid brightening of the ZnE pulp.
Table 8-1. The Development of the Light Absorption Coefficient at pH 6.0,50°C and Different Peracetic Acid Concentrations
! Tirne (min) 1 C, (m'kg) at different peracetic acid concentrations
1. Development of the Kinetic Mode1
Typid chromophoric structures in pulps include conjugated lignin macromolecules,
a d o n y l aromaîic moieties and quinones [29-301. The oxidation of lignin-like material by
peracetic atid has ben studied, mostly with model cornpounds [29-38 1. The overall reaction
pathways which occur during peracetic acid bleaching of wood pulps can be sumrnarized by
the following three general categories:
1. Hydroxylation of the aromatic rings of lignin by electrophilic substitution, resulting in the
formation of hydroquinones [30-341. The hydroquinones can either be destroyed to colourIess
water soluble products via electrophilic ring opening [30,3 11 or be further oxidized to
conjugated quinones, which represent another chromophoric structure [3 1-34]. Kawamoto
et al. [3 11 studied the oxidation of biphenyl lignin model compounds with peracetic acid at
pH 5.5. They found that highly conjugated quinones were formed and that tiirther destruction
O
[fa]: 0.0329 moVL
2.8 1
[Pa]: 0.0493 mol/L
2.8 1
[Pa]: 0.0658 moVL
2.8 1
of these conjugated quinones was a relatively slow process. These hishly conjugated quinones
may be formed by condensation of quinonoid intermediates via a Diels-Alder mechanism f 391.
2. Conjugated quinones, both originally present, and formed fiom Route 1 above can be
fûrther oxidized to usually colourless and water soluble carboxylic acids via the Baeyer-
Villger reaction 13 1-33 1.
3. Lignin structures containing an a-carbonyl group are oxidized via the Baeyer-Villiger
reaction 135-381. 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. It was
also found that a ketone is somewhat less reactive than an aldehyde. For example,
acetoguaiacone is signi£icantly less 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. 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].
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. Peracetic acid (CH,CO,H) is a strong electrophile [29,30,34,39]. When the pH is
in the range of 1 to 6, peracetic acid , rather than peracetate anion (CHJO,') is the dominant
species (the pKa of peracetic acid is 8.2). Therefore, electrophilic attack is the main
mechanism. When the pH is substantially higher than 8.3, the strongly nucleophilic peracetate
anion (CH,COJ [33,35,4042] is the dominant species. As a result, a nucleophilic attack is
expected to be the main reaction mechanism at high pH. It was established that
hydroxylation of the aromatic rings proceeds via the electrophilic mechanism 130-341, while
the Baeyer-Villiger reaction takes place through a nucleophilic attack [35-381. Because of
these facts, 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.
In principle, the Baeyer-VilIiger oxidation could take place at general acidic
conditions. However, experimentd results show that a high concentration of strong acid is
required, For exarnple, it was reported f43-461 that high concentrations of suIfùnc acid and
perchloric acid catalyse the Baeyer-Villiger reaction. However, in the absence of a high
concentration of strong acid, the Baeyer-Viiliger oxidation is expected to be slow under acidic
conditions due to the low nucleophilicity of the undissociated peracid. 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]. Sarkanen and Suniki 1471 found that the amount of side-chah oxidation via the
Baeyer-ViIliger oxidation remains smd at a low pH when they treated Douglas-fir meal with
10% peracetic acid in an aqueous solution. Similarly, Ishikawa et al. [37] treated
acetoguaiacone with 8% peracetic acid at 35°C and found that the oxidation of
acetoguaiacone is quite slow. However, at a high peracetic acid concentration, high
temperature, and an extended reaction time, the Baeyer-Villiger reaction may account for part
of the substrate consumed, as was observed by Nirnz and Schwind 1351. Based on these
results, we assume that peracetate anion, not peracetic acid, is mainly responsible for the
Baeyer-Villiger oxidation in the system we studied.
Based on these identified reaction pathways, the kinetic mode1 shown in Figure 8-2
is proposed for peracetic acid brightening of ozone delignified sofkwood kraft pulp.
The model in Figure 8-2 shows that the chromophoric Iignin macromoIecule C,, is
eIectrophilicdly attacked by peracetic acid CH,CO,H via the hydroxylation route, leading to
the formation of either colourless products (Cp) or conjugated quinones (Ca, as discussed
previously. Therefore, C, is consumed in two cornpetitive reactions, with k, and k2 as their
rzte constants respectively. The conjugated quinones, C,, both the newly formed and those
originally present, are oxidized to water soluble carboxylic acids via the Baeyer-Villiger
reaction by peracetate anion CH,CO;, represented by the rate constant k,. FinalIy, the a-
carbonyl containhg chromophores, C,, are destroyed via the Baeyer-Villiger mechanism by
CH,CO;, with a rate constant of k,.
It is assumed that the reactions discussed in Figure 8-2 are first order with respect to
the peracetic acid concentration and the chromophore concentration. This 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. Therefore, based
on the model described in Figure 8-2, the following rate equations of peracetic acid
brightening are obtained:
- -- dC1 - (k, + kJ C, [C%CO,H] d t
- -- dC2 - $ C, [CH&O;] - \ C , [CH$O,H] dt
-- dC3 = k4C, [ C H p , ] dt
Peracetic acid concentration, [CH,CO,H], and peracetate anion concentration, [CH,CO,],
are related to the total titrable peracetic acid concentration [CH3C0,H], as in Equations (4)
and (5), with M beinç the ratio of the proton concentration to the dissociation constant of
peracetic acid, i.e. [H+]/K,.
Since the concentration of peracetic acid, [CH,C03H], and that of peracetate anion,
[CH$%], are constant at a fixed pH and temperature, Equations (1) to (3) can be simplified
as:
M where k; = k, - [CH-,C03H], 1 +M
Equations (6) to (8) can be solved analyticaily as:
AIso the sum of a11 the different chromophore concentrations at any time during the
course of the peracetic acid treatment equals to the total chromophore concentration. C,
which is known experimentally, i.e.
With the knowledge of the disappearance rate of total chromophore concentration
under different conditions, 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]. The sarne technique was applied to determine
the kinetics of chlorination.[48,49].
Equations (1 3) to (16) show that there are seven unknown variables: ki, ki, kj, k;,
C,, C , and C,, 3 equations, (13), (14) and (15) and 56 data points in the fom of equation
(16). in order to start the search algorithm, it is needed to provide initial values for six of the
variables, with the seventh being fixed by equation (16).
2, Estimation of the Initial Values
2.1, Estimation of CSiand k,
Figure 8- 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, the higher
initial reaction rate in this pH region must be related to the higher peracetate anion
concentration. Since it has ben show that a-carbonyl compounds, represented by C,, react
easily with peracetate anion accordinç to the Baeyer-Villiger mechanism [35-381, while the
oxidation of conjugated quinones proceed slowly in aqueous solutions [3 11, it was assumed
that in the initial phase the Baeyer-Villiger oxidation of a-carbonyl chromophoric structures
is the dominant reaction at a higher pH.
In order to better quanti@ the initial reaction rate, fùrther cxperiments were done to
characterize the light absorption coefficient development during the first 4 minutes at pH 7.0
and 50°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, the shortest time possible with our
experimental set-up, shows that the light absorption coefficient decreases rapidly fiom 2.81
to 1.75 m2/kg. Therefore, the initial a-carbonyl group concentration, C,i , was estimated as
0.96 m'kg fiom the difference of the initial total chromophores, Ci , of 2.8 1 m2/kg and the
sum of C,i and C, of 1.85 m2kg estimated by extrapolating the initial four points in Figure
8-3 to zero time.
Only a vety rough estimate of the rate constant k; can be obtained fiom the data in
Figure 8-3, because the reaction of the cc-carbonyl chromophores with peracetic anion appears
to be essentially complete at the first data point of 5 seconds. However, in order to generate
a first order estimate of the initial value of k; for the optimization procedure it was assumed
that 99% of the a-carbony1 chromophores initially present, C,,, disappeared in the first five
seconds. Following Equation (1 5). we estimated a k; of 6x1 0 min-'. Furthemore, we
calculateci that k, is approximately 2x 10' LImoLmin, by taking into consideration of the pKa,
pH and the total peracetic acid concentration. Since it is realized that the calculated value of
k, of 2x10" L/mol.min is only a first order estimate, the initial value of k, for the optimization
procedure will be varied by two orders of magnitude around 2x10' Llmo1.min in order to
evaluate the sensitivity of the procedure to this initiai guess of k,.
2.2. Estimation of CZi and k,
Since oxidation of both conjugated quinones, Cr and a-carbonyl containing
chromophores, C,, at pH 1.0 is insignificant due to the very low peracetate anion
concentration, the hydroxylation, which is achieved by peracetic acid and represented by
reactions k, and k2, can be considered the ody reactian pathway tu remove chromophures at
this pH. Figure 8-1 shows that the chromophore removal is negligible after 50 minutes of
reaction at pH 1 .O, so it is reasonable to assume that the hydroxylation reaction is completed
within 50 minutes at this condition. Also because the actual concentration of peracetic acid
is essentially the sarne when the pH is increased fiom 1.0 to 6.0, it is assumed that the
hydroxylation reaction at pH 6.0 is also completed within 50 minutes. As discussed earlier,
the Baeyer-Villiger oxidation of a-carbonyl containing chromophores is a fast reaction with
k, being about 2x10' L/mol.min, so that it takes less than one minute to complete this
oxidation at pH 6.0. Based on the above analysis, it can thus be concluded that after 50
minutes at pH 6.0 the decrease in the light absorption coefficient is mainly due to the
destruction of conjugated quinones, C, by reaction with peracetate anion, CH,CO,: i.e.
Equations (6), (7) and (8) reduce to:
Therefore, the initial concentration of conjugated quinones, 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
minutes. From this plot shown in Figure 8-4 it follows that C, is 0.57 m'kg and k; is 0.00 145
min1. Substitution of k; to Equation (1 1) yields k, of 4.7 L/mol.min. With C, of 0.96 m'/kg
(shown in the previous section) and C , of 0.57 m'kg, the estimate for C,i is calculated as
2.3. Estimation of k, and k,
The values of k , and k2 were estimated using the results obtained at pH 1 .O, shown
in Figure 8-1. Since the peracetate anion concentration, [CH,CO,], is extremely low at pH
1 .O, both of the Baeyer-Villiger pathways c m be neglected, as discussed earlier. Therefore,
both k; and k; wili be set equal to zero at pH 1 .O. As a result, Equation (1 6) can be simplified
An application of the exponential decay data fitting technique yields Equation (1 9) to mode1
the data points at pH 1 .O in Figure 8- 1 as:
C = 1.602 + 1.205 e'0-'06' (19)
From a cornparison of Equations (1 8) and ( 1 9), it follows that:
k; and (1 --) CIi = 1.205 k;+ k;
By solving Equations (20) and (21), one obtains a k; of 0.100 min-' and a k; of 0.0062 min-'.
Taking into consideration the pH and the total concentration of peracetic acid in Equations
(9) and (IO), k, and k2 are estimated as 2.03 and 0.126 L/mol.min, respectively.
3. Modelling Results
With the estimation of the initial values of C,i, CZi, C,i, k,, k,, k, and k,, it is now
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] . The
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. The procedure was
considered converged when, for each data set at a fixed pH and peracetic acid concentration,
the surn of squares changed by less than O. 1% between iterations. To ensure that the
optirnised set of parameters indeed represented the unique solution of the kinetic modei for
the present data, the most uncertain parameter, k,, was varied by two orders of magnitude
around the estimated value, while the other rate constants were varied by a factor of two. 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 optimized results are Listed in Table 8-2. It shows that k, is much higher than the
other rate constants, confhing that the oxidation of a-carbonyl containing chromophores,
C,, is a fast reaction. This is in agreement with the findings by McDonough [333 that
acetoguaiacone reacts much faster than apocynol and vanillyl alcohol during peracetic acid
treatment at a pH of 6 to 9. Table 8-2 also shows that k, is comparable to k , so their
reaction rates largely depend on the concentrations of CH,CO,H and CH,CO;. Thus it is
expected that the oxidation of conjugated quinones, CL proceeds slowly due to the lower
concentration of CH,CO,- at a pH lower than 7.0, as was supported by Kawamoto et al. [3 11
who showed that fùrther oxidation of the conjugated quinones fomed via the hydroxylation
pathway to colourIess products is quite slow at pH 5.5 [3 Il.
An example of a companson between calculated and measured light absorption
coefficients at pH 7.0 is given in Figure 8-5. It is apparent that the proposed kinetic model
gives a good description of the development of the Iight absorption coefficient dunng
peracetic acid brightening of the ozone detignified pulp used in this study.
Table 8-2. The Kinetic Parameters Obtained by the Hook and Jeeves Search Algorithm at 50°C for the Brightening of ZnE Pulp
With the optirnized kinetic parameters, the concentration-tirne profiles of the three
different chromophores, C,, G, C, and the total chromophore concentration C was predicted
at a pH of 3.O,7.O and 10.0. The results are plotted in Figures 8-6 to 8-8 respectively. At pH
3 in Figure 8-6 the destruction of chromophores C , is completed d e r about 50 minutes while
around 40% of the a-carbonyl containing chromophores, C,, are destroyed at 90 minutes.
However, the concentration of the conjugated quinones, G, increases slightly over the course
of the reaction. The behaviour of the C, 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. At pH 7.0 in Figure 8-7, the oxidation
of the a d o n y l containing chromophores, C,, is accomplished within a few seconds, while
the CI chromophores are also removed within one hour. The degradation of conjugated
quinones, however, is still incomplete at 90 minutes at pH 7. At a higher pH of I O in Figure
8-8, it c m be seen that now the oxidation of conjugated quinones, Cb is complete in almost
20 minutes. 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]. It can also be noticed that
Estimated
Optimized
Initial chromophore concentration (m" /kg)
Rate constants (L/mol. min)
C3i
0.96
1-01
CIi
1.28
1.26
C3
0.57
0.54
kt
2.03
k3
4.7
3.33
kz
0.126
k4
20000
17700 0.17
at pH 1 0 the destruction rate of chromophores C, is significantly reduced due to a much
lower concentration of peracetic acid. Thus, although both quinones, C2, a-carbonyl
containing chromophores, C,, are efficiently removed at pH 10, the overalI degree of
chromophore removal is much less than that at pH 7.0 because the initial concentration of C,
chromophores is larger than that ofthe C, chromophores. This explains the experimental fact
that optimum brightness gain can be obtained at a neutral pH ranse.
CONCLUSIONS
Based on reaction pathways identified in literature, a kinetic model for peracetic acid
brightening of a solvent-assisted ozone delignified pulp has been developed. The kinetic
equations can adequately describe the developrnent of the light absorption coefficient of pulp
under conditions of constant pH and peracetic acid concentration. The model includes three
parailel reactions, namely hydroxylation, oxidation of conjugated quinones, and oxidation of
carbonyl containing iignin stmctures, which are responsible for the overall removal of
chromophores, and thus for the decrease in the light absorption coefficient of the bleached
pulp. The reaction rate of each of the three reactions is dependent on the pH during the
peracetic acid treatment. At pH 3 only hydroxylation is significant. At pH 7, both the
hydroxylation and oxidation of carbonyl containing lignin structures is complete, while oniy
the conjugated quinones are rernaining when the treatment is extended beyond 50 minutes
at 50°C. A fitrther increase in pH to 10.0 significantly retards the hydroxylation rate, which
explains the smalter removal of chromophores at this pH as compared to that at pH 7.0.
ACKNOWLEDGMENT
NSERC's financial support in the form of a Strategic Grant is greatly appreciated.
REFERENCES
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Anderson, J. R., 8. Amini and W. Wilkinson, On-site Generation and Use of Peroxy Acids in Chemical Pulp Bleaching, Prepnnts, the 8 1'' CPPA Annual Meeting, Tech. Sect., CPPq Montreal, 1995, p. B59.
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Liebergott, N., Di-per process: Time for a peracid delignification and bleaching, Proceedings, Preprints, SI* CPPA Annual Meeting, Tech. Sect., CPPA, Montreal, 1995, p. BI57
Song, J., Peroxyacid Bleaching of Conventional, MCC and RDH Kraft Pulps, Ph.D thesis, North Caroline State University, USA, 1992
Springer, E. L. and J. D. McSweeny, Treatment of Softwood Kraft Pulps with Peroxymonosulfate Prior to Oxygen Delignification, Tappi J., 76(8): 194 (1 993)
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Troughton, N., F. Desprez and J. Devenyns, Peracids: The Pathway to High Brightness TCF Kraft Pulps, Proceedings, 1994 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technolog Transfer Inc. Amelia Island, FL, sec. 1 0- 1.
Devenyns, J., F. Desprez and N. Troughton, Peroxygen PrebIeaching and Bleaching Technologies for Step-Wise Conversion fiom Conventional Chlorine Bleaching via ECF toTCF, TAPPI 1993 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 341.
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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, 1993 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., HHI, SC, sec. 8-1
Bailey, C. W. and C. W. Dence, Peroxyacetic Acid Bleaching of Chernical Pulp, Tappi J., 49(1):9 (1966).
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Rapson, W. H., and C. B. Anderson, BIeaching in Five Stages to Asymptotic Limit Using Only One Oxidant and Sodium hydroxide, 1985 International Pulp Bleaching Conference, Quebec, 1985, p. 227 .
GeUerstedt, G., Peracid Technology Review, Preprint, 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology, Raleigh, N.C., March 3, 1993.
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Moldenius, S. and B. Sjogren, Kinetics Models for Hydrogen Peroxide Bleaching of Mechanical Pulps, J. Wood Chem. Tech. 2(4):447(1982)
Allison, R.W. and K. L. Graham, Peroxide Bleaching of Mechanical Pulp Fractions fiom Radiata pine, JPPS 1 5(4):.Jl45(1989)
Wright, P. and J. Abbot, Kinetic Models for Peroxide Bleaching under alkaline Conditions. Part 1 : One and Two Chromophore Models, J. Wood Chem. Tech. 1 l(3): 349(1991)
Wright, P., Y. Ginting and J. Abbot, Kinetic Models for Peroxide Bleaching under Alkaline Conditions. Part 2: Equilibrium Models, J. Wood Chem. Tech. IS(1): 1 1 l(1992)
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Germgird, U. and A. Teder, Kinetics of Chlorine Dioxide Prebleaching, Trans. Tech. Sect., CPPq 6, TR3 1 ( 1980)
Hooke, R. and T.A. Jeeves, Direct Search Solutions of Numerical and Statistical Problems, 3. Assoc. Comp. Mech., 8(2):2 12(196 1 )
Kang, G. J., Y. Ni and A. R. P. van Heiningen, Mechanism of Cellulose Protection in a Novel and Selective Ozone Pulp Bleaching Process, Preprints, the 82nd CPPA Annual Meeting Preprints, Tech. Sect., CPPq Montreal, 1996, p. B303
Greenspan, F. P. and D. G. Mackellar, Andysis of Aliphatic Peracids, Analy. Chem., 20(I 1): 1061 (1 948)
Rapson, W. H., The Role of pH in Bfeaching, Tappi J., 39(5):284 (1956).
Sarkanen, K. V-and C. H. Ludwig, Lignins, Wiley Interscience, N. Y., 197 1, p.459
Boeseken, J. and R. Engleberts,, Proc. Acad. Sci. Amsterdam, 34, 1292(193 1); 35 750(1932)
Kawamoto, H., H. Chang and H. Jameel, Reaction of Peroxyacids with Lignin and Li& Model Compounds, Proceeding, the 8& International Symposium on Wood and Pulping Chemistry, Helsinki, Finland, June, 1995, p.3 83.
Strumila, G. and H. Rapson, Reaction Products of Neutra1 Peracetic Acid Oxidation of Model Lignin Phenols, Pulp & Paper Canada, 76(9):72(1975)
McDonough, T. J. M., Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Aikaline Solutions, Ph.D Thesis, University of Toronto, Canada (1 972)
Henderson, G.G. and R. Boyd, Oxidation of Monohydric Phenols with Hydroçen Peroxide, J. Chem. Soc., 97, l659(l9 10)
Nimz, H. H. and H. Schwind, Oxidation of Monomeric Lignin Model Compounds with Peracetic Acid, CelluIose Chem. Technof ., 13, 3 5 (1 979)
Hatakeyarna, H., J. Nakano, and N. Migita, Lignin, XLVII. Origin of Succinic Acid as An Oxidation Product of Lignin with Peracetic Acid, J. Chem. Soc. Japan, Ind. Chem. Sect., 68, 972(1965)
Ishikawa, H., T. Oki and K. Ohkubo, Oxidative Decomposition of Lignin, V. The Degradation by Peracetic Acid of Aromatic Compounds Stmcturally Related to Vanillyl Alcohol Elements Present in Sofbood Lignin, J. Japan Tappi, 20, 435(1966)
Kinoshita, Y., T. Oki and H. Ishikawa, Oxidative Degradation of Guaiacylglycerol with Peracetic Acid, J. Japan. Wood Res. Soc., 13, 3 19 (1 967)
Farrand, J. C., Peroxyacetic Acid Oxidation of 4-Methylphenols and Their Methyl Ethers, Ph.D. Thesis, Institute of Paper Chemistry, Appleton, Wisconsin, USA, 1969
Jencks, W. P. and J. Camuolo, Reactivity of Nucleophilic Reagents toward Esters, J. Am. Chem. Soc., 82, 1778 (1960)
HassalI,C. H., Organic Reactions, Vol. 9, p.73, A. Roger (ed.), John Willey & Sons Ltd., New York, 1957.
Yasuhiko, S., Organic Peroxides, p.437, W. Ando, (ed.), John Willey & Sons Ltd., New York, 1992.
Lefiler, J. E, Hydroperoxide Oxidation of a-dicarbonyl Compounds,J. Org. Chem., 16, 1785 (1951)
Doering, W. von E. and L. Speers, The Peracetic Acid Cleavage of Unsymmetrical Ketones, J. Am. Chem. Soc., 72(12):% 15 (1 950)
Friess, S. L., Reaction of Per Acids II: The Reaction of Perbenzoic Acid with Simple Cyclic Ketones, J. Am. Chem. Soc., 7I (7):257l (1 949)
Marker, R. E., E. Rohmann, H. M. Crooks, E. L. Whittle, E. M. Jones, and D. L. Turner, Oxidation Products of Sarsapogenin Pregnanetriol-3,16,20, J. Am. Chem. Soc., 62(2): 5 25 ( 1 940)
Sarkanen, K. V. and J. Suzuki, Delignification by Peracetic Acid, Studies on Oxidative Delignification Mechanisms, Tappi J. 48(8):459 (1 965)
Mackinnon, J., Dynamic Simulation of the First Two Stages of a Kraft Softwood Bleach Process, M. Eng. Thesis, McGill Univ., Canada, 1989
Ni, Y., G. J. Kubes and A. R. P. van Heiningen, Chlorination Kinetics of Kraft Pulp, JPPS, 21(1):J30 (1 995)
Figure 8-1. 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,CO,Hl of 0.0493 m o n )
Figure 8-2. The proposed kinetic mode1 of peracetic acid brightening
3.0
0 . 0 ~ . , I [ i = 1 ~ l ~ l ' ~ ' 0!0 0-5 1.0 1.5 2 0 2 5 3.0 3.5 4.0 4.5
Time (min)
Figure 8-3. Estimation of C, and k, (50°C, p H 7.0, [CB,CO,H] of 0.0493 m o n )
O 100 150 200 250 300 350
Time (min)
Figure 8-4. Estimation of CIi and k, (50°C, pH 6.0, [CH,CO,H] of 0.0493 moVL)
3.0 1
O 10 M 30 40 50 ô0 70 80 90 100
Time (min)
Figure 8-5. Cornparison of mode1 predictions and experimental results (SOT, pH 7.0, [CH,CO,HJ of 0.0493 m o a )
O 20 40 60 80 100
Time (min)
Figure 8-6. Predictions of the development of C,, C,, C, and C (5OUC, pH 3.0, [CH3C03H] of 0.0493 moVL)
O 20 40 60 80 1
Time (min)
Figure 8-7. Predictions of the development of C,, C,, C, and C (50°C, pH 7.0, [CH,CO,H] of 0,0493 moVL)
Time (min)
Figure 8-8. Predictions of the development of C,, C,, C, and C (SOT, pH 10.0, [CH3C03H] of 0.0493 m o n )
CHAPTER 9
CONCLUSIONS
GENERAL SUMMARY
This thesis focuses on fundamental and practicai aspects of peracetic acid brightening
of softwood kraft pulps.
A final TCF brightening sequence of PaEop has been developed for a solvent assisted
ozone delignifieci and oxidative extracted (ZnEo) Hemlock kraft pulp. 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.s with
charges of 2% ozone, 1.5% Pa and 0.5% hydrogen peroxide. The brightness, 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. The optimum conditions for the peracetic acid
and Eop stages have been detemined. Those for the Pa stage are: a peracetic acid charge of
1.5%, 20% pulp consistency, 60°C, a neutral pH and 3 hours. The optimum conditions for
the reinforced Eop stage are: 20% pulp consistency , 95"C, 60 psi oxygen pressure, 90 min
with 0.5% H202 , 1.5% NaOH and 0.1% MgSO,. No chelation chemicals are required for
this TCF bleaching sequence.
Tt has been shown that under typical peracetic acid bleaching conditions, peracetic acid
is consumed by three wasteful side reactions in addition to the desired oxidation reactions
with pulp. These unwanted reactions are: i) spontaneous decomposition, ii) hydrolysis and
iii) transition meta1 catalysed reactions.
The addition of the chelating agent DTMPA to a dilute peracetic acid solution
effectively suppresses the metal catalysed reactions of peracetic acid. ln a pH range of 5.5 to
8.2 the hydrolysis is negligible and the peracetic acid consumption is mainly due to
spontaneous decomposition, while between pH of 8.2 to 9.0 the peracetic acid consumption
is due to spontaneous decomposition and alkaline hydrolysis.
The kinetics of the spontaneous decomposition of peracetic acid were developed. It
was found that the spontaneous decomposition is second-order with respect to the total
peracetic acid concentration ([CH,CO,H]J. The present experimental resuIts are well
described by the developed kinetic equation.
pH is one of the important factors which determine how peracetic acid is consumed.
It was found that the spontaneous decomposition reaches its maximum rate at pH 8.2, while
both the hydrolysis and metal ion catalysed reactions increase as the pH increases. At pH 1 0.5
or higher the hydrolysis becomes dominant when the metal ion catalysed reactions are
minimized by the addition of DTMPA.
The kinetics of the alkaline hydrolysis of peracetic acid were also developed. When
these kinetics are combined with those of the spontaneous decomposition developed earlier,
the consumption of peracetic acid and hydrogen peroxide by decomposition reactions can
be accurately predicted. It was also found that the addition of MgSO, at pH 9.5 leads to
formation of a precipitate of Mg(OH), which reduces the rate of transition metal catalysed
reactions but enhances that of the hydrolysis of peracetic acid. With the addition of 6 g/L
MgSO, at pH 9.5, the hydrolysis is rnainly responsible for the consumption of peracetic acid.
The transition metal ion induced peracetic acid decomposition and the effect of the
addition of cheiants/additives on the decomposition were studied under the typical peracetic
acid pulp bleaching conditions. The results show that a significant amount of peracetic acid
c m be wasted when metal ions are present, resulting in Iess efficient bleaching. The metal ion
induced decomposition may proceed via a radical mechanism; however, the oxidation and
reduction cycle involving Mn(I1) and MnO,- prevails when manganese is present in the
peracetic acid solution at a pH of around 6.
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. This is explained by assuminç that the more stable complexes
of DTPA or DTMPA with Cu2+ and ~ e ) ' do not catalyse the decomposition reactions, while
the less stable DTPA-M~I~' complex does, and by the fact that only rnanganese participates
in an oxidation-reduction cycle, while Cu2+ and ~ e ~ ' do not.
A close inverse relationship between peracetic acid decomposition and pulp brightness
development was observed and confinned at constant pH and peracetic acid condition. A
chelation pretreatment stage for pulps with a high metal ion content, especially manganese,
lads to improved subsequent peracetic acid bleaching, while for pulps with a low content of
metal ions chelation prior to Pa treatment may not be necessary. The addition of sodium
pyrophosphate effdvely deactivates the metal ions and consequently improves the bleaching
performance. However, the addition of some chelants, such as DTPA, to the peracetic acid
bleach liquor may rmlt in poor bleaching due to the fact that peracetic acid is consumed by
wastefùl reactions with DTPA.
Oqgen is the main gaseous product produced fiom the decomposition of peracetic
acid under typical brightening conditions, Le. pH 7 and 60°C. One mole of oxygen is
generated per two moles of oxidants (peracetic acid and hydrogen peroxide) consumed. At
a relatively low pH (-5) CO2 rnay also be formed fiom the wastefùl reactions at a
stoichiometry of 3 moles of oxidant consumed per mole of CO2 released. Thus, based on the
stoichiometry of formation of OZ and COZ the arnount of oxidant consumed in wastehl
reactions can be calculated fiom the generation of these two gases. Furthermore, 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.e. charge minus residual) and that what is
wasted.
It is found that the pulp bnghtness gain is directly related to the peracetic acid
consumption in the oxidation of pulp, 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, the pulp viscosity loss is uniquely related to the loss in oxidant as measured by the
0, and CO, generation. These findings contribute a powerfbl tool for control and
optimization of an industrial peracetic acid stage.
Finaliy, a kinetic model for peracetic acid brightening of an ozone delignified pulp was
developed based on the reaction pathways identified in the literature. The kinetic equations
adequately describe the development of the light absorption coefficient of pulp at conditions
of constant pH and peracetic acid concentration. The model is based on three parallel
reactions, namely hydroxylation, oxidation ofconjugated quinones, and oxidation of carbonyl
containing lignin structures, which together are considered to be responsible for the overall
removal of chromophores, and thus for the decrease in the light absorption coefficient. The
reaction rate of each of the three reactions is dependent on the pH during the peracetic acid
treatment. At pH 3 only hydroxylation is significant. At pH 7, both the hydroxylation
reactions and oxidation of carbonyl containing lignin structures go to complet ion, while the
conjugated quinones are the only residual chromophores when the treatment is extended
beyond 50 minutes at 50°C. A fiirther increase in pH to 10.0 sigiificantly retards the
hydroxylation rate, resulting in a reduced removal level of chromophores compared to that
at pH 7.0.
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
APPENDIX
THE COMPUTER OPTIMIZATION PROGRAM FOR THE KINETIC STUDY OF PERACETIC ACID BIUGHTENING
C ******************************************************************* C * MAIN PROGRAM FOR THE MODELLING OF BLEACHING PROCESS * c ******************************************************************* C C ******************************************************************** C * THE ROLES OF THE MAIN PROGRAM ARE : * C * - READ IN AND MANIPLLATE DATA * C * - EXECUTE HOOKE AND JEEVES SEARCH ALGORITHM * C * - PRn\ST OUT TEMPORARY AND FINAL PARAMETER VALUES * C * - P W OUT FINAL COMPARISONS * c ******************************************************************** C
MAL CKE(12,l O),CKC(12,1 O),TIM( 12,l O),PAO( 12),PHV(I 2),TEMP(12) REAL CK 1 ( 12,l O), C D ( 1 2,l O), CKC0( 1 2,l O) REAL PARVAL(1 Z),PARSTP(I 2), STPSZL(12) REAL NEWStTM,CURSUM,PAROLD INTEGER STUMP,NLTMPAR,NUMSET,NUMPT,LSTONE,PARCNT MTEGER FLAG(lZ),SETNUM( 12), SETPTS( 1 2), TAG,FTAG,SET
C C c C # VARIABLE DICTIONARY # C # # C # CKE -- ARRAY OF EXPERTMENTAL ABSORPTION COEFFICIENTS # C # CKC -- ARRAY OF CALCULATED ABSORPTION COEFFICIENTS # C # TIM -- ARRAY OF THE SAMPLING TLME # C # PA0 -- ARRAY OF TOTAL PERACETIC ACID CONCENTRATION # C # PHV - ARRAY OF pH # C # TEMP -- ARRAY OF TEMPERATURE # C # CKI - ARRAY OF CK ACCOUNTED BY CARBONYL STRUCTURE # C # CK2 -- ARRAY OF CK ACCOUNTED BY HYDROXYLATION # C # CKCO -- ARRAY OF CK ACCOUNTED BY QUINONE STRUCTURE # C # NUMSET-- NUMBER OF DATA SETS # C # SETNUM-- ARRAY OF SET NUMBERS OF SIZE NUMSET # C # SEPTS-- ARRAY OF NT-JMBER OF POINTS IN EACH DATA SET # C # NUMPT -- NUMBER OF DATA POINTS # C # NUMPAR-- NUMBER OF PARAMETERS TO BE FIT # C # PARVAL- ARRAY OF CURRENT PARAMETER VALUES # C # PARSTP- ARRAY OF CURRENT STEP SIZES # C # STPSZL- ARRAY OF STEP SIZES USED TO KEEP TRACK OF # C # PROPER SEARCH METHOD # C # CURSUM-- REFERENCE SUM OR THE LOWEST SUM OF SQUARES # C # OF DIFFERENCE IN LIGNIN CONTENT # C # NEWSUM-- SUM OF SQUARES CALCULATED USING NEW #
C # PARAMETER C # C # VALUES, TO BE COMPARED WITH CURSUM # C # FLAG -- ARRAY OF TAGS IDENTIFYING WHICH PARAMETERS # C # HAVE CHANGED VALUE IN THE ITERATION # C # P, STUMP,LSTONE,PARCNT,TAG,FTAG # C # - COUNTERS OR TAGS # C C# C C TAG TO BYPASS ITERATION SCHEME C
TAG=O C C SET NLRLiZBER OF ITERATIONS C
WRITE(* ,12) 12 FORMAT(1 X,'NtTMBER OF ITERATIONS :')
RE AD(*, *) 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 READ INITIAL PARAMETER VALUE GUESSES AND STEP S E E S AND PRINT C
READ(2,*) NLTMPAR DO 30 I= 1 ,NUMPAR
READ(2, *) PARVAL(I), PARSTP(1) FL AG(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=', 1 2X,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 SET SUMTOO C
CURSUM=O. O C C CALL SUBROUTINE TO CALCULATE CK AND DETERMINE SUM OF C SQUARES C FOR THE INITIAL BASE CASE C
C ALL SUMCwSET,NUMPT,TMCKE,PAO,PW,TEMP,PARVAL, PARSTP, + CKC,CURSUM)
C C GO TO THE END OF PROGRAM IF TAG = 1 C
IF (TAG .EQ. 1) GOTO 999 570 CONTINUE
PARCNT= 1 C C START SEARCH PATTERN C
DO 5 15 I= 1 ,NUMPAR PARCNT=I
C C INCREASE THE PARAMETER VALUE BY CORRESPONDING STEP SEE C
PAROLD=PARVAL(PARCNT) PARVAL(PARCNT)= PAROLD+PARSTP(PARCNT)
C C 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
PAROLD=PARVAL(l) STPSZL(I)=PARSTP(I)
C C DECREASE THE PARAMETER VALUE BY STEP SIZE C
PARVAL(I)=PAROLD-STPSZL(1)-PARSTP(1) 531 C0NTNL.E C C CHECK IF NEW PARAMETER VALUE IS GREATER THAN O C
IF (PARVAL(1) .GT. 0.0) GûTO 532 STPSZL(I)=STPSZL(I)/8 PARVAL(I)=PAROLD- STPSZL(1)-P ARSTP(1) GOTO 53 1
532 CONTINUE GOTO 55 1
550 CONTINUE STP SZL(I)=P ARSTP(1)
C C DECREASE PARAMETER VALUE BY STEP SIZE C
PARVAL(PARCNT)=PAROLD-PARSTP(PARCNT) 533 CON- C C CHECK IF NEW PARAMETER VALUE IS GREATER THAN O C
IF (PARVAL(1) .GT. 0.0) GOTO 534 STPSZL(I)=STPSZL(I)/8 P ARVAL(I)=P AROLD-STPSZL(1) GOTO 533
534 C ONTrn 551 CONTINUE C C CALCULATE NEW SUM OF SQUARES C
CALL SUMCAL(NUMSET,NUMPT,TIM,CKE,PAO,PHV,TEMPARVAL,PARSTP, + CKC,NEWSUM)
C C CHECK IF NEW MTNlMUM HAS BEEN FOUND C
IF (NEWSUM .LT. 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 5 74 PARSTP(I)=PARSTP(I)*0.90
574 CONTINUE FLAG(I)=O
575 CONTrNuE C C PRINT MTERMEDIATE PARAMETER VALUES AND SUM OF SQUARES C
STUMP=LSTONE- 1 WRITE(*,80 1) 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,'= ', 1 X,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(*, 12 1) 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(*, 1 20) W T E ( * , 125)
125 FORMAT(IX,' TIME(MTN) CKC CKE') WRITE(*, 1 28)
1 28 FO RMAT(1 X,' --------- -------- ---------- ') WRITE(*, 120) DO 130 I=I,NUMSET
DO 132 J=l,NUMPT WRITE(*, 13 1) TIM(I,J),CKC(I,J),CKE(I,J)
13 1 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(1 X,' TIME(MIN) CK 1 CK2 CKX') 1 68 FORMAT(1 X,' ---------- ---------- ---------- --------- '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 * SUBROUTINE SUMCAL TO CALCULATE THE SUM OF SQUARES OF * C * THE DIFFERENCE OF EXPERIMENTAL AND MODEL PREDICTED DATA * C **************************************************#***************** C
SUBROUTINE SUMCALO\IUMSET,NUMPT,TIM,CKE,PAO,PHV,TEM, +PARSTP,CKC,SUM) REAL CKE(12,l O),CKC( 12, I O),TIM(12,1 O),PAO( I2),PHV( 12),TEMP( 1 2) REAL PARVAL(I2),PARSTP(12),CURSUM,CKO,C 10,C20,C 1 ,C2,C3,C4 REAL M,K 1 ,K2,K3,K4,R,CKALPHA,CK 1 CK2 RVTEGER NUMSET,NUMPT
C C SETSUMSTOO C
SUMl=O.O SUM=O.O
C C SET KNOWN PARAMETERS C
CKO=2.8 1 R=8.3 14 CKALPHA=PARVAL(6) CK1 CK2~2.8 1 -CKALPHA
C C CALCULATE CKC FOR ALL DATA SETS C
DO 840 I= 1 ,NUMSET PA=PAO(I) CKC(I,1)=2.8 1 M= 1 O* *(8.2-PHV(1)) DO 850 J=2,NUMPT
C 1 O=PARVAL( 1 ) C20=CK 1 CK2-C 1 O 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 1 O*EXP(-(KI +K2)*TIM(I,J)) C2=C 1 0iK2*EXP(-(K 1 +K2)*TIM(I,J))/(K3-K 1 -K2) C3=(C2O+C 1 O*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 SUM THE SQUARES OF DIFFERENCES OF CKC AND CKE C
SUM I=SUM 1 +(CKC(I,J)-CKE(I,J))* *3 SUM=StTMl
850 c o w m
840 CONTINUE RETURN END
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