Cellulose protectors for improving ozone bleaching - review

See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/227337294
Cellulose protectors for improving ozone bleaching - Review
Article  in  Wood research · January 2004
CITATIONS
14
READS
617
3 authors:
Some of the authors of this publication are also working on these related projects:
Complex utilization of bark extractives View project
Printed functional layers for hybrid perovskite solar cells (VEGA 2019/2022) View project
Michal Jablonsky
Slovak University of Technology in Bratislava
186 PUBLICATIONS   463 CITATIONS
SEE PROFILE
Milan Vrška
SEE PROFILE
Svetozar Katuscak
SEE PROFILE
All content following this page was uploaded by Michal Jablonsky on 02 June 2014.
The user has requested enhancement of the downloaded file.

71
WOOD RESEARCH
49 (4): 2004
CELLULOSE PROTECTORS FOR IMPROVING
OZONE BLEACHING - REVIEW
MICHAL JABLONSKÝ, MILAN VRŠKA, SVETOZÁR KATUŠČÁK
FACULTY OF CHEMICAL AND FOOD TECHNOLOGY, DEPARTMENT OF CHEMICAL TECHNOLOGY OF
WOOD, PULP AND PAPER, SLOVAK REPUBLIC
ABSTRACT
Cellulose protectors (CPs) are able to eliminate an influence of degradating processes
in ozone bleaching. Published literature reviews on using ozone in bleaching of pulps, issued
till the year 1992, have not contained any systematic classification of cellulose protectors by
chemical groups. It has not dealt with evaluation of the effect of applied additives on the change
of viscosity, kappa number and brightness either. In this work, we present a survey of the additives
applied in ozone bleaching from the year 1963 to 2003. Used CPs were systematically classified
to 7 main chemical groups. The influence of used additives is evaluated on the basis of the change
of viscosity, kappa number and the brightness compared to the ozone bleaching without additives
as for their positive and negative effect. The group of carboxylic acids can be ranked among the
most effective additives, as regards the aspect of viscosity, elimination of lignin and brightness.
Inorganic additives that were assessed usually have no positive influence on the protection of
cellulose against degradation.
KEY WORDS: ozone bleaching, cellulose protector, degradation, additive, hydroxyl radical
INTRODUCTION
The use of ozone as a bleaching agent for chemical pulps has been studied extensively in the 70th.
Ozone has been used either or with other bleaching agents in a multistage process, primarily to replace
delignification stages that use elementary chlorine. Ozone is a strong oxidating agent that reacts with
almost any organic material, including lignocellulosic material. Ozone reactions are thought to be
selective toward lignin. Ozone plays a key role in the development of closed bleaching processes. The
negative influence of ozone in pulp bleaching lies in its degradative effect on cellulose. A decrease
of polymerizing degree can be avoided by the use of additives that work as cellulose protectors
(Liebergott and Lierop 1978, Medwick et al. 1992). The mentioned authors published a thorough
review in 1978, which discussed the effects of pulp consistency, pH, time and temperature on the
ozonization of hardwood and softwood kraft and kraft-oxygen pulps in great detail.
Additional publications by Liebergott et al. (1992a, 1992b) and Medwick et al. (1992)
from 1992 were literature reviews which covered: studies on ozone bleaching according to pulp
type, the effect of main reaction variables, studies on carbohydrate/preserving additives and
pretreatments, studies of bleaching sequences containing ozone, and pilot plant studies. They may
Drevo 4_2004 041123.indd 71Drevo 4_2004 041123.indd 71 04/11/23 1:16:11 PM04/11/23 1:16:11 PM

72
be seen as a survey of cellulose protectors for improving ozone bleaching. They also introduce
changes in viscosity, degree of delignification (kappa number) and brightness.
Ozone as an individual oxidative reagent when compared with polysaccharides reacts 105
times faster with substances of the lignin type. The reason for degradation of a number of reactions
is formation of hydroxyl (free) radicals (Ragnar et al. 1997, Zhang et al. 2000, Ragnar 2000).
These radicals are the results of reactions with lignin. The cause of the radical formation in ozone
bleaching has been attributed to the self-decomposition of ozone (Zhang 1994). This reaction is
slow in acidic media. However, the selectivity of the reaction of hydroxyl radical with carbohydrate
of lignin type, expressed as a ratio of rate constants kL / kc of radicals, is less than 5-6 (Hoigne
and Bader 1983a and 1983b, Ek et al. 1989, Solinas et al. 1994, Zhang 1994, Bouchard et al. 1995,
Ragnar 2000). The radicals formed in reactions between ozone and lignin or in the decomposition
of ozone in water promote the unwanted attack of ozone on carbohydrates, which may cause
an unacceptable decline in strength properties. The purpose of many studies, listed above, is to
identify conditions that minimize the ozone-carbohydrate reactions.
The aim of this work is the systematic classification of used additives by the chemical groups
and evaluation of the influence of CPs in ozone bleaching. In this work, we evaluate present the
additives applied in ozone bleaching from the year 1963 to 2003.
Mechanisms of cellulose protection
Contribution concerns of the use of cellulose protectors in ozone bleaching, usually mention
various mechanisms for the protection of cellulose against degrading reactions. Many authors
explain the protective influence of used additives just as a hypothesis of possible mechanisms for
the protection of cellulose, or an effect in the process of pulp ozonization. Mechanisms of cellulose
protectors effects are as follows:
1. The protective effect on degradation of the cellulose may be interpreted as the scavenging
of hydroxyl radicals (Walling and El-Taliwai 1973, Pan 1984, Lachenal and Bokstrom 1986,
Kang et al. 1995, Gierer and Zhang 1993, Magara et al. 1994, Cogo et al. 1999, Bouchard et
al. 2000).
2. Physical factors such as changed solubility of oxidation agents in the presence of CPs and
changes in the pKa of functional groups, primarily in lignin (Lindholm 1987).
3. Selective adsorption - CPs may be adsorbed on cellulose surfaces, thereby acting as
a protective barrier for the cellulose. In this way they presumably coat and reduce the surface
area of the available cellulose (Cogo et al. 1999, Allan et al. 2000, Van Heiningen and
Violette 2003).
4. The formation of compounds between CPs and cellulose which prevent the degradation of
cellulose (Katuscak et al. 1971a and 1971b and 1972a, Kamishima et al. 1977a).
5. Decreased accessibility of cellulose to oxidation agents (decreased swelling in the presented
CPs in cellulose) (Mbachu and Manley 1981, Kamishima et al. 1982a and 1982b, Bouchard
et al. 2000, Roncero et al. 2003a).
6. CPs may lead to a diminution in the extent of the oxidant to the preferred reaction site (Allan
et al. 2000).
7. The reduction of carbonyl groups to hydroxyl groups or the removal of carbonyl groups also
stabilizes the cellulose chain (Osawa and Schuerch 1973).
8. The removal of metal cations (Soteland 1977, Kamishima et al. 1977b, Lachenal and
Bokstrom 1986, Chirat 1993).

73
Ozone bleaching with additives
A lot of articles has been devoted to finding an additive or a pretreatment that would protect
the cellulose and make the ozone react more preferentially with the lignin in the fiber. In this
investigation, the application of various inorganic and organic additives before and during ozone
bleaching in order to improve pulp qualities was studied. These substances are expected to
decrease or completely eliminate the degradative reactions that affect the decrease of selectivity
and efficiency of ozone bleaching. The main task of additives is to prevent the degradation of
polysaccharides. Besides the cellulose protection, they have also studied from the viewpoint
of increasing brightness and the amount of eliminated lignin. Some of the additives are able to
prevent the degradation of polysaccharides, but on the other side, their application to the system
of ozone bleaching lacks the required elimination of lignin or brightness rise, or both.
Tables 1 and 2 summarize the results obtained. They present additives which were
experimentally applied in ozone bleaching in the period from 1963 to 2003. The applied additives
are ranked according to chemical groups. None could be identified as preventing degradation
of cellulose while promoting the removal of a large portion of the lignin. The influence of used
additives is evaluated on the basis of the positive(+) or negative(-) effect on the following main
characteristics of pulps: the change of viscosity, the change of lignin content expressed as the
change of kappa number and the change of brightness compared to the ozone bleaching without
additive use.
Used CPs were systematically classified to 7 main chemical groups, namely to alcohols,
carboxylic acids, carbonyl compounds, organic compounds with nitrogen, other organic
compounds and inorganic compounds.
Ozone bleaching with alcohols
Alcohol impregnation of pulp before ozone bleaching has been shown to be very effective
for improving selectivity (Bouchard et al. 2000). Most of examinated alcohols have a positive
effect on removal lignin and at the same time they prevent carbohydrate degradation during
ozone bleaching. The most applied alcohols are methanol and ethanol (Fujii et al. 1986, Berg et
al. 1995, Griffin and Van Heiningen 1998, Bouchard et al. 2000, Hägglund 2001, Meredith 1980,
Kamishima 1982a and 1985a, Solinas et al. 1994 and 1997). The addition of methanol (80-100%
on pulp) showed some chance of commercial application (Kamishima et al. 1977b). There is a
continuous research to find a way of improving application of additives to decrease their amount
in ozone bleaching stage. One possibility lies in the addition of additives to the ozone gas stream
(Bouchard et al. 2000). Other frequently evaluated additives are CPs such as ethylene glycol,
isopropanol and tert-butyl alcohol (Meredith 1980, Solinas et al. 1994 and 1997, Murphy and
Norris 1996, Hägglund 2001, Kassebi and Gratzl et al. 1982). Ethylene glycol increases the
selectivity during ozone delignification much more than methanol, and its effect is optimal at pH
3 and 35wt% ethylene glycol in the reaction system (Johansson et al. 2000). In the presence of
tert-butyl alcohol an improvement, was found in efficiency and selectivity of ozonization (Zhang
et al. 1997b, Cogo et al. 1999). According Hoigne and Bader (1983a and 1983b) tert-butyl alcohols
inhibits the radical decomposition of ozone by scavenging hydroxyl radicals. Cogo et al. (1999)
found that tert-butyl alcohol was not consumed during the ozonization process.

74
Tab. 1: Organic compound added to pulp before and in combination with an ozone stage.
Structure
according to
chemical
groups
Cellulose protector
Change of
viscosity
Change of
Kappa number
Change of
brightness
References
Methanol + + +
6,9,21,27,28,32-35,36,
37,39-42,48,59,62,64,
83,84,89,95
Ethanol + + + 33,40,62,83,84,93,102
Propanol + + + 62,83,84
Isopropanol + + + 44,62,83,84
1-butanol + + 15,62
2-butanol + + 62
tert-butyl alcohol + + + 15,28,62,103
2-methyl-1-propanol + + 62
1-pentanol - 62
1-hexanol + 62
Monoalcohols
1-heptanol + 62
Ethylene glycol + + 28,32,62,64,83,84
Propanediol + + 64
Dialcohols
1,4-butanediol + + 64
Glycerol + + 64
Diethylene glycol + + 64
Pentaerythritol + + 64
2-butoxyethanol + + 64
2-(2-butoxyethoxy)ethanol + + 64
Alcohols
Otheralcohols
2-(2-ethoxyethoxy)ethanol + + 64
Formic acid + ;- +; - + ; - 35,40,60,79,95
Acetic acid + ; - +;- +
3,6,9,15,33,35,40,44,49,
50,60,65,68,79,89,95,10
3
Propionic acid - ; + + + 10,4,38,40
n-Butyric Acid + + + 38,40
i-Butyric acid + + + 35,40
n-Valeric acid + + + 35,40
Monocarboxylicacids
i-Valeric acid + + + 35,40
Oxalic acid + + ;- +
1,7,10,11,15,20-22,
33,35,36,38-42,55,56,
74,75,95
Malonic acid + ; - + + 35,40
Succinic acid + - ; + + ; - 35,40
Glutaric acid + + + 35,40
Dicarboxylicacids
Adipic acid + ; - + - ; + 35,40
Maleic acid + ; - + - ; + 35,40
Unsaturated
acids Itaconic acid - - - 35,40
Glycolic acid + ; - + + 35,40
Lactic acid + ; - + + 35,40
Malic acid + + + 15,35,40
Hydroxy-
carboxylic
acids
Tartaric acid + ; - + + 1,35,40
Glyoxylic acid + + + 35,40
Pyruvic acid + ; - + + 35,40
Carboxylicacids
Ketocar-
boxylic
acids
Levulinic acid + + + 35,40
Change of viscosity – positive effect on viscosity, increases viscosity against to ozone bleaching without additive.
Change of Kappa number – positive effect on Kappa number, decreases Kappa number against to ozone bleaching without additive.
Change of brightness – positive effect on brightness, increases brightness against to ozone bleaching without additive.
(+ positive effect, - negative effect)

75
Tab. 1: cont. - Organic compound added to pulp before and in combination with an ozone stage.
g p p p g
Structure
according to
chemical groups
Cellulose protector
Change of
viscosity
Change of
Kappa number
Change of
brightness
References
Tetrahydrofuran 15
Ethylene oxide 53
1,4-Dioxane + - 15,87,92
Trioxane 26
Ether
compounds
Diethylether 15
Methylethyl ketone - 33,40
Acetone + - + 95
Carbonylcompounds
Ketone
compounds
Formaldehyde + - + 33,89,95
Salicylic acid + - - 95
Benzoic acid +; - - +; - 35,40,95
Terephthalic acid - + - ; + 35,40
p-hydroxybenzoic acid + ; - - - ; + 35,40
Vanillic acid + ; - - ; + - ; + 35,40
Aromaticacids
Protocatechuic acid + ; - - - ; + 35,40
Formamide - 33,40
p-Phenylenediamine - 33,40
Pyridine - 33,40
N-cyclohexyl
pyrrolidinone
+ + 88
Thriethanolamine - 33,40
N-methyltaurine + + + 77,78
Urea-Methanol + + 33,40
Tetramethylurea + + 88
DTPA - ; + + + 1,84,85,95
EDTA + - + 1,11,69,95
Mg-EDTA - 33,40
DMF + + 15,33,40
Organiccompoundswithnitrogen
Nitromethane - - ; + 67

76
Tab. 1: cont. - Organic compound added to pulp before and in combination with an ozone stage.
Structure
according to
chemical groups
Cellulose protector
Change of
viscosity
Change of
Kappa number
Change of
brightness
References
Ethyl acetate 15
Methyl acetate - + 67,80
Acetic anhydride - 33,40
Sodium acetate - 33,40
Mg-Acetate - 33,40
Peracetic acid + + + 19,69,76,79,101
Carboxylic
derivates
Sodium formate 26
Galacturonic acid - 33
Glucose + 33,40
Methyl cellosolve + 33,40
Dextrin - 33,40
CMC - 33,40
Dialdehyde starch 33,40
Derivatesof
saccharides
Starch - 33,40
Lignin - 23,24,26,33,40,59
p-benzoquinone + 33,40
Hydroquinone - 33,40
Antraquinone + - + 77,78
Other
aromatic
compounds
Pyrogallol + 33,40
Diethylenetriamine-
pentaphoshonic acid
1
DMSO + - + 5,15,33,40,44,55,56,95
Hexadecyl trimethyl
ammonium bromide
- + + 17
Nonyl trimethyl
Ammonium
bromide
- + + 17
Dodecyl trimethyl
ammonium bromide
- + + 17
Benzoyl peroxide + 51
Di(tert-
butyl)peroxide
+ 51
Sulfamic acid + + + 33,95
Thioglycolic acid 53
Citric acid + + + 1,95
L-cystine 53
Lecithin 33,40
Acrylonitrile 53
Butadiene 53
DABCO 26
Polyethylene glycol 26
Cyclohexan - 16
Benzene - 16
NH2NH2 - 33,40
Otherorganiccompounds
Otherorganiccompounds
NH2OH.HCl + 33,40

77
Tab. 2: Inorganic compounds compound added to pulp before and in combination with an
ozone stage.
Structure Cellulose protector
Change of
viscosity
Change of
Kappa number
Change of
brightness
References
Na2CO3 + + - 26,95
MgCO3 - 33,40
MgSO4 - 33,40
MnSO4 - 33,40
FeSO4 - 33,40
CuSO4 - 33,40
Na2SO4 - 33,40
(NH4)2SO4 - 33,40
Al2(SO4)3 - 33,40
NaBH4 -; + 33,40,96
KBH4 + 96
MgO - 33,40
NaCl - 33,40
CoCl2 - 33,40
ZnCl2 - 33,40
Mn(NO3)2 - 33,40
NH4NO3 + 33,40
KI - 33,40
I2 - 33,40
P4 + + + 98
KH2PO4 - 33,40
Na2B4O7 - 33,40
Na2SiO3 - 33,40
(NH4)6Mo7O24.4H2O + + + 2,72
NaClO + + + 66,99
ClO2 + + + 12-14,63,90,91
Na2O2 + 51
H2O2 + 51,76
H2SO4 + + +
33,50,56,60,68 other
studies
H2SO5 + + 101
H3PO3
1
H3BO3 + - + 95
HNO3 + + 6,68
Cl2
91,99
SO2 + - 56
CO2 - + - 95
NO + + 81,82
Inorganiccompounds
NO2 + + + 50,70

78
Ozone bleaching with carboxylic acids
Most of used carboxylic acids shows positive effect on viscosity, the removal of lignin
and brightness. According to Kamishima et al. (1982a and 1985a) among twenty-seven organic
compounds, the oxalic acid belongs to the most effective and its optimum pH is 2. It provides high
yield of bleached pulps and also increases contents of α-cellulose and the pentosans (Kamishima
et al. 1983b). Contrary Lidholm (1989) declared that oxalic acid improved the high consistency of
ozone bleaching process only slightly. Mbachu and Manley (1981) found that acetic and formic acid
pretreatments use less ozone to reach a given kappa number than does a sulfuric acid-treated pulp.
The positive effect on the change of viscosity can be seen in these substances from the group of
monocarboxylic acids (n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid) and dicarboxylic
acids as oxalic, succinic and glutaric acid (Kamishima 1982a and 1985a). Improvement of selectivity
has been attributed to the decreased accessibility of the cellulose to ozone due to a very poor swelling
effect of organic acids (Mbachu and Manley 1981, Lachenal and Bokstrom 1986). Mentioned acids
also provides possibility of radical scavenging (Tibbling 1993, Zhang et al. 1997b).
Ozone bleaching with carbonyl compounds
Cogo et al. (1999) found that acetone and formaldehyde (Tibbling 1993) increased selectivity
ozone bleaching. The presence of dioxane does not significantly change the ozone reaction
efficiency but leads to a dramatic reduction of cellulose degradation (Van Heiningen et al. 1994).
Ozone bleaching with aromatic acids
Aromatic acids with more amount of ozone added achieve a better brightness but don't avoid
degradation of cellulose (Kamishima et al. 1977b and 1982a). Aromatic acids like salicylic acid
(Vivero and Blanco 2001), benzoic acid, p-hydroxybenzoic acid, vanillic and protocatechuic acid
seem to prevent viscosity loss somewhat (Kamishima et al. 1977b and 1982a).
Ozone bleaching with organic compounds with nitrogen
Presence of N-methyltaurine derivate at a proper amount of added ozone has favourable effect
on pulp yield, its brightness, kappa number, viscosity and strength properties (Rutkowski and
Szopinski 1983 and 1984). Tan and Solinas (1996) examined the effect of N-alkylated compounds
such as N-cyclohexyl pyrrolidinone and tetramethylurea and proved a significant improvement in
viscosity, kappa number reduction and the brightness development. Other compounds like urea-
methanol, DMF (Kamishima et al. 1977b and 1982a), EDTA (Chirat 1993, Parthasarathy and
Glenn 1995, Vivero and Blanco 2001) and DTPA (Solinas et al. 1994 and 1997, Vivero and Blanco
2001) were used as effective CPs in ozone bleaching. According to Kamishima et al. (1977b)
the formation of clathrate compounds between urea and cellulose prevented the degradation
of carbohydrates. The application of a chelant such as DTPA or EDTA before the ozone stage,
however, was shown to be best at pH 3 rather then pH 8, suggesting that acid sequestering is best
for metal ion removal (Allison 1982).

79
Ozone bleaching with other organic compounds
The pulp bleached with ozone and peracetic acid improved the ozone bleaching and strength
properties (Rothenberg et al. 1975, Fuhrman et al. 1997, Parthasarathy and Glenn 1995, Rautonen
1997). Peracetic acid reacts with lignin and opens up the pulp fiber structure (Parthasarathy and
Glenn 1995). Citric acid (Andersson et al. 1992, Vivero and Blanco 2001) and sulfamic acid
(Kamishima et al. 1977a, Vivero and Blanco 2001) has been shown to be effective for improving
selectivity and efficiency of ozone bleaching. Organic compounds such as glucose, methyl
cellosolve, p-benzoquinone, pyrogallol, hydroxylamine hydrochloride (Kamishima et al. 1977a
and 1985a) benzoyl peroxide, di(tert-butyl)peroxide (Liebergott 1973), DMSO (Kamishima
et al. 1977a and 1985a, Allison 1985, Lindholm 1987 and 1989, Cogo et al. 1999, Vivero and
Blanco 2001) and antraquinone (Rutkowski and Szopinski 1983 and 1984) may be preventing to
carbohydrates degradation at ozone bleaching. Eckert et al. (1978) found that in the presence of
cationic surfactant process of lignin removal and brightness enhancement may be improved.
Ozone bleaching with other inorganic compounds
Inorganic compounds that are effective cellulose protectors in oxygen delignification offered
no protection during ozone bleaching. Addition of small amounts of metal such as iron, copper
and nickel salts increased cellulose degradation (Kamishima et al. 1977a, 1985b). Some chemicals
(e.g. magnesium compounds) used as an effective cellulose protector in oxygen delignification
are defeated in ozone bleaching. Heavy metals may decompose the ozone, leaving apportion of it
unavailable to react with lignin (Soteland 1974). The addition molybdates (Ragnar 2000, Agnemo
2002) and P4 (Wang et al. 1997) to an ozone bleaching stage can markedly reduce the viscosity
loss and increase the brightness of the pulp. Inorganic acids like sulfuric acid (among studies),
boric acid (Vivero and Blanco 2001), Caro´s acid (Zhang et al. 1995), nitric acid (Pan 1984)
seemed to have positive effect in ozone bleaching. Combination of ozone and chlorine dioxide
may allow reduction of chlorine dioxide amount and improvement of ozone bleaching (Tsai 1990,
Chirat 1995, Chirat and Lachenal 1997, Chirat et al. 1997, Millar et al. 2002, Toven 2003). Acidic
peroxide treatment at pH 2 - 3 just prior to ozone application also improved the efficiency of an
ozone delignification stage (Liebergott et al. 1973, 1992b, Rothenberg et al. 1975).

80
CONCLUSION
Base on the presented list of additives, we can conclude that the positive effect on the change
of viscosity can be seen in these substances: alcohols in general, from the group of carboxylic
acids mainly monocarboxylic acids (n-butyric acid, i-butyric acid, n-valeric acid, i-valeric acid)
and dicarboxylic acids (oxalic, succinic and glutaric acid). The next group with a positive effect
is made up of carbonyl compounds (1,4-dioxan, acetone, formaldehyde) and aromatic acids
(salicylic, benzoic, p-hydroxybenzoic, vanillic and protocatechuic acids). Inorganic substances
show in general a negative effect on the change of viscosity.
As for the aspect of kappa number, alcohols, carboxylic acids, organic compounds with
nitrogen (N-cyclohexyl pyrrolidinone, N-methyltaurine, urea-methanol, tetramethylurea, DMF)
have the positive effect on its decrease.
The whole group of carboxylic acids considerably affects the change of brightness.
From the other groups of substances we can mention complex making reagents (EDTA,
DTPA) and, for example, sulfuric acid that prevents the catalytic effect of transition metals in the
formation of free radicals and decomposition of ozone.
With regards for viscosity, elimination of lignin and brightness agents the group of carboxylic
acids proved to be the most efficient substances.
Theproblemoffindingacheapeffectivecommercialinhibitorofcarbohydratedepolymerization
during ozone delignification is still actual. Further verification of the additives effect has been
continuing within the VEGA project.
ACKNOWLEDGEMENTS
The authors express their thanks to the VEGA agency for financial support of the project No.
1 / 0061 / 03.

81
REFERENCES
1. Andersson, L., Basta, J., Holinger, L., Hoeoek, J. EP 0512590 (Nov., 11, 1992).
2. Agnemo, P., 2002: Reinforcement of oxygen-containing chemicals with molybdates. J. Pulp
Paper Sci. 28(1): 23-25.
3. Allan, G.G., Aravamuthan, R.G., Christien, C., Petersen, B.A., Marshall, A.J., 2000: Selective
adsorption: a new approach to cellulose protection during bleaching. Cellulose Chem.
Technol. 34: 509-524.
4. Allison, R.W., 1982: Efficient ozone and peroxide bleaching of alkaline pulps from pinus
radiata. Appita 36(1): 42-46.
5. Allison, R.W., 1985: Effects of temperature and chemical pretreatment on pulp bleaching with
ozone. CPPA/TAPPI Int. Pulp Bleaching Conf. (Quebec City) Proc.: 47-53.
6. Berg, A., Janssen, W., Balle, S., Kunz, R.G., Klein, W. U.S. pat. 5385641 (Jan., 31, 1995).
7. Bokstrom, M. U.S. pat. 6458242 (Oct., 1, 2002).
8. Bouchard, J., Nugent, M.H., Berry, R.M., 1995: The role of water and hydrogen ion
concentration in ozone bleaching of kraft pulp at medium consistency. Tappi J. 78(1): 74-82.
9. Bouchard, J., Morelli, E., Berry, R.M., 2000: Gas-phase addition of solvent to ozone bleaching
of kraft pulp. J. Pulp Paper Sci. 26(1): 30-35.
10.Chang, Y.S., Yun, R.Y., Tsai, H.C., 2002: Study on the ozonal bleaching of hard to-bleach
chemical pulps. Taiwan J. For Sci. 17(1):67-74.
11.Chirat, C., 1993: Protection of cellulose during ozone bleaching. Paperi ja Puu 75(5): 338-
342.
12.Chirat, C., 1995: Other ways to use ozone in a bleaching sequence. Pulping Conference:
Proceedings (TAPPI): 415-420.
13.Chirat, C., Lachenal, D., 1997: Other ways to use ozone in a bleaching sequence. Tappi J.
80(9): 209-214.
14.Chirat, C., Lachenal, D., Angelier, R., Viardin, M.-T., 1997: (DZ) and (ZD) bleaching:
Fundamentals a application. J. Pulp Paper Sci. 26(6): J289-J292.
15.Cogo, E., Albert, J., Malmary, G., Coste, C., Molinier, J., 1999: Effect of reaction medium on
ozone mass transfer and applications to pulp bleaching. Chemical Engineering Journal 73:
23-28.
16.Djamal, S., Kojima, Y., Kayama, T., 1984: Bleaching of Red Lauan chemical pulps with ozone
and hydrogen peroxide. Japan Tappi 38(11): 1136-1143.
17. Eckert, R.C. U.S. pat. 4119486 (Oct., 10, 1978).
18.Ek, M., Gierer, J., Jansbo, K., Reitberger, T., 1989: Study on selectivity of bleaching with
oxygen-containing species. Holzforshung 43(6): 391-396.
19.Fuhrman, A., Li, X., Rautonen, R., 1997: Influence of ozone and peracetic acid on pulp and
effluent characteristic. Pulping Conference: Proceedings (TAPPI): 615-624.
20.Fujii, T., Kamishima, H., Akamatsu, I., Nakayama, S., 1983) Influence of addition of oxalic
acid on the rate of cellulose degradation and delignification during ozone bleaching of kraft
pulp. Japan Tappi 29(6): 422-427.
21.Fujii, T., Kamishima, H., Akamatsu, I., 1986a: Oxygen-ozone-hydrogen peroxide bleaching
sequence of kraft pulp. Kami Pa Gikyoshi 40(8): 743-748.
22.Fujii, T., Kamishima, H., Akamatsu, I., 1986b: Liquid-phase ozone bleaching of kraft pulp.
Kami Pa Gikyoshi 40(5): 477-482.
23.Gierer, J., 1982: The chemistry of delignification. A general concept. Holzforschung 36(1):
43-51.

82
24.Gierer, J., 1982: The chemistry of delignification. A general concept. Part II. Holzforschung,
36(2): 55-64.
25.Gierer, J., Zhang, Y., 1993: The role of hydroxyl radicals in ozone bleaching processes. 7th Intl.
Symp. On Wood and Pulping Chem. 2, Beijing, P.R. China: 951-960.
26.Godsay, M.P., 1985: Ozone-cellulose studies: Physico-chemical properties of ozone oxidized
cellulosic and lignocellulosic materials. 239 f. Thesis (Ph.D. Ciência e Engenharia de
Polímeros) Polytechnique Institute of New York, New York, USA.
27.Griffin, R., Van Heiningen, A.R.P., 1998: The development of delignification on lignin-
cellulose selectivity during ozone bleaching. J. Pulp Paper Sci. 24(4): 111-115.
28.Hägglund, K., 2001: Ozone bleaching with organic solvents as additive: pulp quality. http://
epubl.luth.se/1402-1617/2001/227/index-en.html.
29.Hoigné, J., Bader, H., 1983a: Rate constants of reactions of ozone with organic and inorganic
compounds in water-I. Non-dissociating organic compounds. Water Res. 17: 173-183.
30.Hoigné, J., Bader, H., 1983b: Rate constants of reactions of ozone with organic and inorganic
compounds in water-II. Dissociating organic compounds. Water Res. 17: 185-194.
31.Jacobson, B., Lindblad, P., Nivelbrant, N., 1991: Lignin reactions affect the attack of ozone
on carbohydrates. International Pulp Bleaching Conference Proceedings, SPCI, Stockholm,
Sweden: 46-58.
32.Johansson, E.E., Lind, J., Ljunggren, S., 2000: Aspects of the chemistry of cellulose
degradation and the effect of ethylene glycol during ozone delignification of kraft pulps. J.
Pulp Paper Sci. 26(7): 239-244.
33.Kamishima, H., Fujii, T., Akamatsu, I., 1977a: Effect of cellulose protectors on ozone
bleaching of kraft pulp. Kami Pa Gikyoshi, 31(9): 664-672.
34.Kamishima, H., Fujii, T., Akamatsu, I., 1977b: Ozone bleaching of kraft pulp in the presence
of methanol as cellulose protector. Kami Pa Gikyoshi 31(10): 669-706.
35.Kamishima, H., Fujii, T., Akamatsu, I., Nakyama, S., 1982a: The effect of organic acids on
carbohydrate protection during ozone bleaching of kraft pulp. Japan Tappi 28(6): 370-375.
36.Kamishima, H., Fujii, T., Akamatsu, I., 1982b: Verification of the effectiveness of methanol
and oxalic acid for carbohydrate protection during ozone bleaching. Mozukai Gakkaishi
28(7): 480-483.
37.Kamishima, H., Fujii, T., Akamatsu, I., 1983a: Factors affecting the carbohydrate protection
of methanol during ozone bleaching of UKP. Mozukai Gakkaishi 29(7): 474-480.
38.Kamishima, H., Fujii, T., Akamatsu, I., 1983b) Effects of oxalic acid on properties of bleached
pulps during ozone bleaching. Japan Tappi 37(5): 438-442.
39.Kamishima, H., Fujii, T., Akamatsu, I., 1984: Mechanism of carbohydrate protection with oxalic
acid and methanol during ozone bleaching of unbleached kraft pulp. Japan Tappi 30(11): 927-935.
40.Kamishima, H., Fujii, T., Akamatsu, I., 1985a: Protective agents for carbohydrates in ozone
bleaching of unbleached kraft pulps. II. Screening of protective agents for carbohydrates in
ozone bleaching. Shikoku Kogyo Gijutsu Shikensho Kenkyu Hokoku (9): 15-30.
41.Kamishima, H., Fujii, T., Akamatsu, I., 1985b: Protective agents for carbohydrates in ozone
bleaching of unbleached kraft pulps. III. Effect of protection agents for carbohydrates on
properties of ozone bleached pulps. Shikoku Kogyo Gijutsu Shikensho Kenkyu Hokoku 17(9):
31-39.
42.Kamishima, H., Fujii, T., Akamatsu, I., 1985c: Protective agents for carbohydrates in ozone
bleaching of unbleached kraft pulps. IV. Protection mechanism of methanol and oxalic acid for
carbohydrates in ozone bleaching. Shikoku Kogyo Gijutsu Shikensho Kenkyu Hokoku 17(9):
40-62.

83
43.Kang, G.J., Ni, Y., van Heiningen, A.R.P., Zhang, Y.J., 1995: Influence of lignins on the
degradation of cellulose during ozone treatment. J. Wood Chem. Tech. 15(4): 413-430.
44.Kassebi, A., Gratzl, J.S., 1982: Nonconventional kraft pulp bleaching-role of ozone. TAPPI
Pulping Conf. (Toronto) Proc.: 327-340.
45.Katuscak, S., Hrivik, A., Mahdalik, M., 1971a: Ozonization of lignin. Part I. Activation of
lignin with ozone. Paperi ja Puu 53(9): 519-524.
46.Katuscak, S., Rybarik, I., Paulinyova, E., Mahdalik, M., 1971b: Ozonization of lignin. Part II.
Investigation of changes in the structure of methanol lignin during ozonization. Paperi ja Puu
53(11): 665-670.
47.Katuscak, S., Hrivik, A., Macak, K., 1972a: Ozonization of lignin. Part III. Stable radicals in
ozonized lignin preparations. Paperi ja Puu 54(4a): 201-206.
48.Katuscak, S., Hrivik, A., Katuscakova, G., Schiessl, O., 1972b: Ozonization of lignin. Part IV.
The course of ozonization of insoluble lignins. Paperi ja Puu (2): 861-870.
49.Kishimoto, T.B., Tsuji, H., Uraki, Y., Sano, Y., 2003: Ozone bleaching of atmospheric acetic
acid hardwood pulp from Betula platyphylla var. japonica Hara. Holzforschung 57(2): 181-
188.
50.Lachenal, D., Bokstrom, M., 1986: Improvement of ozone prebleaching of kraft pulps. J. Pulp
Paper Sci. 12(2): J50-J53.
51.Liebergott, N. NO pat. 127410B (Jun.,18.,1973).
52.Liebergott, N., van Lierop, B., 1978: The use of ozone bleaching and brightening wood pulp,
Part I. Chemicals pulps. Tappi Seminar Notes Oxygen, ozone and peroxide bleaching. New
Orleans, Nov. 9: 90.
53.Liebergot, N., van Lierop, B., Skothos, A., 1992a: A survey of use of ozone in bleaching pulps,
Part 1.Tappi J. 75(1): 145-152.
54.Liebergot, N., van Lierop, B., Skothos, A., 1992b: A survey of use of ozone in bleaching pulps,
Part 2.Tappi J. 76(2): 117-124.
55.Lindholm, C.-A., 1987: Effect of pulp consistency and ph in ozone bleaching. Paperi ja Puu 3:
211-218.
56.Lidholm, C.-A., 1989: Effect of pulp consistency and pH in ozone bleaching. V. Various
pretreatments and additives in low and high consistency bleaching. Cellulose Chem. Technol.
23: 307-319.
57.Lindholm, C.-A., 1990: Effect of dissolved reaction products on pulp viscosity in low-
consistency ozone bleaching. Paperi ja Puu 72(3): 254-256.
58.Magara, K., Ikeda, T., Tomimura, Y., Hosoya, S., 1994: Accelerated degradation of cellulose
by lignin during ozonolysis. Japan Tappi 40(10): 1152-1154.
59.Magara, K., Ikeda, T., Tomimura, Y., Hosoya, S., 1998: Accelerated degradation of cellulose
in the presence of lignin during ozone bleaching. Journal of Pulp and Paper Sci. 24(8): 264-
268.
60.Mbachu, R.A.D., Manley R.St.J., 1981: The effect of acetic and formic acid pretreatment on
pulp bleaching with ozone. Tappi J. 64(1): 67-70.
61.Medwick, V.B.Jr., Gratzl, J.S., Singh, R.P., 1992: Delignification and bleaching of chemical
pulps with ozone: a literature review. Tappi J. 77(3): 207-213.
62.Meredith, M.D. U.S. pat. 4229252 (Oct., 21, 1980).
63.Millar, H., Ruiz, J., Freer, J., Baeza, J., 2002: Modification of a mill DEOPDD sequence:
Improvement in the stage for combination of ozone (Z) and chlorine dioxide (D) the (ZD)
EOPDD sequence of softwood kraft-pulp-oxygen pulp. J. Chil. Chem. Soc. 48(1): 29-33.
64.Murphy, T.H., Norris, R.G. U.S. pat. 5507913 (Apr., 16, 1996).

84
65.Nimz, H.H., Berg, A. U.S. pat. 5074960 (Dec., 24, 1991).
66.Okubo, K., Oki, T., Ishikawa, H., 1982: Bleaching of thermomechanical pulp by NaOCl-ozone
system and characteristic properties of bleached pulp. Japan Tappi 36(8): 807-814.
67.Osawa, Z., Schuerch, C., 1973: The action of gaseous reagents on cellulosic materials. I.
Ozonization and reduction of unbleached kraft pulp. Tappi J. .46(2):79-84.
68.Pan, G.Y., 1984: Studies on ozone bleaching. (1: Effect of pH, temperature, buffer systems
and heavy metal ions on stability of ozone in aqueous solution. J. Wood Chem. Technol. 4(3):
367-387.
69.Parthasarathy, V. R., Glenn, R.F. U.S. pat. 5387317 (Feb., 7, 1995).
70.Patt, R., Welkener U., 1985: Bleaching of baggase soda pulp with nitrogen dioxide an ozone.
Holzforshung 39(5): 305-310.
71.Ragnar, M., Tord, E., Torbjőrn, R., 1997: The initial hydroxyl radical yield reactions of ozone
with lignin and carbohydrate model compounds a kinetic study. ISWPC: A5-A10.
72.Ragnar, M., Tord, E., Torbjőrn, R., 1999: Radical formation in ozone reactions with lignin and
carbohydrate model compounds. Holzforschung 53( 3): 292-298.
73.Ragnar, M., 2000: On the importance of radical formation in ozone bleaching. Ph.D. Thesis,
Kungliga Tekniska Högskolan (KTH), Stockholm, Sweden.
74.Roncero, M.B., Colom, J.F., Vidal, T., 2003a: Cellulose protection during ozone treatments of
oxalic acid oxygen delignified Eucalyptus kraft pulp. Carbohydrate Polymers 51: 243-254.
75.Roncero, B.M., Colom, J.F., Vidal. T., 2003b: Why oxalic acid protects cellulose during ozone
treatments? Carbohydrate Polymers 52(4): 411-422.
76.Rothenberg, S., Robinson, D.H., Johnsonbaugh, D.K., 1975: Bleaching of oxygen pulps with
ozone. Tappi J. 58(8): 182-185.
77.Rutkowski, J., Szopinski, R., 1983: Use of ozone in bleaching kraft pulp. Przeglad Papier
39(8): 283-287.
78.Rutkowski, J., Szopinski, R., 1984: Investigations on bleaching of sulfate pine with pulp
ozone. Cellulose Chem. Technol. 18(3): 323-333.
79.Saake, B., Lehnen, R., Schmekal, A., Neubauer, A., Nimz, H.H., 1998: Bleaching of formacell
pulp from aspen wood with ozone and peracetic acid in organic solvents. Holzforshung 52(6):
643-650.
80.Schuerch, C., 1963: Ozonization of cellulose and wood. J. Polym. Sci.: Part C. (2): 79-95.
81.Solinas, M., Murphy, T.H. WO9317178 (Sept., 2, 1993).
82.Solinas, M., Murphy, T.H. U.S. pat. 5364503 (Nov., 15, 1994).
83.Solinas, M., Murphy, T.H., van Heiningen, A.R.P., Ni, Y. WO 9410377 (May, 11, 1994).
84.Solinas, M., Murphy, T.H., Van Heiningen, A.R.P., Ni, Y. U.S. pat. 5685953 (Nov., 11, 1997).
85.Soteland, N., 1977: The effect of ozone on mechanical pulps. Pulp Paper Can. 78(7): 45-48.
86.Soteland, N., 1974: Bleaching of chemicals pulps with oxygen and ozone. Pulp Paper Can.
75(4): T153-T158.
87.Takagi, H., Kayama, T., 1980: Alkali-dioxan pulping. (2: Bleaching with ozone and hydrogen
peroxide. Japan Tappi 34(2): 204-210.
88.Tan, Z., Solinas, M. U.S. pat. 5529662 (Jun., 25, 1996).
89.Tibbling, P. WO9323608 (Nov., 25, 1993).
90.Toven, K., 2003: Paper properties and swelling properties of ozone-based ECF bleached
softwood kraft pulps. Tappi J. 2(2): 3-7.
91.Tsai, T.Y. U.S. pat. 4959124 ( Sep.,25.,1990).
92.Van Heiningen, A.R.P., Adriaan, R.P., Ni, Y. U.S. pat. 5354423 (Oct., 11, 1994).
93.Van Heiningen, A.R.P., Ni, Y. WO9736040 (Oct., 2, 1997).

85
94.Van Heiningen, A.R.P., Violette, S., 2003: Selectivity improvement during oxygen
delignification by adsorption of a sugar-based polymer. J. Pulp Paper Sci. 29(2): 48-53.
95.Vivero, R., Blanca, M., 2001: Incremento de la Selectividad en el Blanqueo con Ozono de una
Secuencia TCF del tipo XOZP. Part II. Aplicación de Aditivos. p.5-11-5-19. www.tdx.cesca.
es/TESIS_UPC/AVAILABLE/TDX-0325103-125233/08CAPITULOS.pdf
96.Wade, R. C. U.S. pat. 3.318.657 (May, 9, 1967).
97.Walling, C., El-Taliwai, G.M., 1973: Fenton´s reagent. II. Reactions of carbonyl compounds
and α, β-Unsaturated acids. J. Am. Chem. Soc. 95(3): 844-847.
98.Wang, H., Shi, Y., Le, L., Wang, S., Wei, J., Chang, S., 1997: POZONE technology to bleach
pulp. Ind. Eng. Chem. Res. 36(9):3656-3661.
99.Wigner, G.A. German pat. 1298875 (Apr., 7, 1969).
100. Zhang, Y., 1994: On the Selectivity of Ozone Delignification during Pulp Bleaching.
Ph.D. Thesis, Kungliga Tekniska Högskolan (KTH), Stockholm, Sweden.
101. Zhang, X.Z., Francis, R.C., Troughton, N.A. U.S. pat. 5411635 (May, 2, 1995).
102. Zhang, X., Z., Kang, G., Ni, Y., Van Heiningen, A.R.P., 1997a: Kinetics of carbohydrate
degradation due to direct attack by ozone. ISWPC p.131-1-131-4.
103. Zhang, Y., Kang, G., Van Heiningen, A.R.P., 1997b: Degradation of wood polysaccharide
model compounds during ozone treatment. J. Pulp Paper Sci. 23(1): J23-J27.
104. Zhang, X.Z., Ni, Y., Van Heiningen, A., 2000: Kinetics of cellulose degradation during
ozone bleaching. J. Pulp Paper Sci. 26(9): 335-339.

86
ING. JABLONSKÝ MICHAL
FACULTY OF CHEMICAL AND FOOD TECHNOLOGY,
DEPARTMENT OF CHEMICAL TECHNOLOGY OF WOOD,
PULP AND PAPER,
RADLINSKÉHO 9,
812 37 BRATISLAVA,
SLOVAK REPUBLIC
e-mail: michal.jablonsky@stuba.sk
ING. VRŠKA MILAN, CSC.
PULP AND PAPER,
RADLINSKÉHO 9,
812 37 BRATISLAVA,
SLOVAK REPUBLIC
e-mail: milan.vrska@stuba.sk
DOC. ING. KATUŠČÁK SVETOZÁR, CSC.
PULP AND PAPER,
RADLINSKÉHO 9,
812 37 BRATISLAVA,
SLOVAK REPUBLIC
e-mail: svetozar.katuscak@stuba.sk
Drevo 4_2004 041123.indd 86Drevo 4_2004 041123.indd 86 04/11/23 1:16:45 PM04/11/23 1:16:45 PMView publication statsView publication stats

Cellulose protectors for improving ozone bleaching - review

Recommended

Recommended

More Related Content

What's hot

What's hot (20)

Similar to Cellulose protectors for improving ozone bleaching - review

Similar to Cellulose protectors for improving ozone bleaching - review (20)

More from Michal Jablonsky

More from Michal Jablonsky (20)

Recently uploaded

Recently uploaded (20)

Cellulose protectors for improving ozone bleaching - review