HYDROGEN PEROXIDE BLEACHING

Peroxide is being used to brighten both mechanical and chemical pulps. Peroxide is not to selectively destroy the chromophoric groups without dissolving lignin. Because of this it is being used to bleach mechanical pulps which have high pulp yield because of retention of almost whole of lignin. Peroxide is also being used to bleach chemical pulps both in ECF and TCF bleaching sequences.

 In ECF bleaching sequences, it is being used in the later stages to enhance the brightness and brightness stability of pulp. In ECF sequences, the use of peroxide has reduced the requirements of ClO2. In TCF sequences H2O2 is used to brighten the oxygen and ozone delignified pulps. Growth in the hydrogen peroxide in chemical pulp bleaching is attributable largely to environmental constraints in the operation of bleach plants. Use of H2O2 reinforced extraction stage enables the proceeding chlorine/chlorine dioxide stage to be operated at lower kappa factor

Reactions of Hydrogen Peroxide

Hydrogen peroxide under alkaline conditions reacts with hydroxyl ion (HO-) to yield per hydroxyl anion (OOH-). H2O2 + OH- OOH- + H2O --------(1) This anion is a strong nucleophile and is primarily responsible for bleaching effect of alkaline hydrogen peroxide. There are two competing reaction in hydrogen peroxide bleaching. The first leads to brightness increase while the second leads to decomposition of hydrogen peroxide into water and oxygen.

 The peroxide decomposition is catalysed by metals present in the bleaching solution and pulp particularly transition metal ions. The decomposition of hydrogen peroxide is first order w.r.t. hydrogen peroxide. It takes place via the following reaction Mn+ + H2O2 HO. + OH- + Mn+1 ----(2) .OH + O.OH O-.2 + H2 O ----(3) O-.2 + H2O2 O2 + HO. + OH----(4) Hydroxy radicals react preferable with phenolic units These react with carbohydrates and degrading it. This depends upon lignin to carbohydrate ratio in the pulp, thus requiring the use of pulp protectors.

Rate of destruction of chromophoric groups follows the equation:

-dNchrom / dt = DKo exp (-Ea /RT) [HOO-] Nchrom ---(5) Nchrom = Chromophore concen.in pulp at a given time [HOO-] = Perhydroxyl anion concentration Ea = Activation energy D = Transfer coefficient from liquid to pulp phase R is gas constant, Ko rate constant & T absolute temp. Per hydroxyl ion formed with reaction of H2O2 with alkali is responsible for bleaching action. Its concentration increases with increase in pH (Fig.1) particularly in the pH range 9-12. The decomposition reaction can be controlled by minimizing the concentration of transition metal ions by the addition of peroxide stabilizers.

Effect of pH on the dissociation of hydrogen peroxide

Effect of Process Conditions

Hydrogen Peroxide Charge:
The brightness of the pulp increases with higher peroxide charge to the extent it is effectively consumed. The brightness gain also depends upon factors such as metal ion removal, liquor carryover, pH, temp. and retention time. TEffect of hydrogen peroxide charge on the development of brightness is shown in Fig.2.

Effect of peroxide charge on the rate of bleaching of an oxygendelignified hardwood kraft pulp bleached with hydrogen peroxide

 The results in Fig.2 show that there is a faster development of brightness in the first hours and then slows down upto 4 hours and then increases slowly upto a reaction time of 14 hours. Higher dose of peroxide gives higher pulp brightness. The increase is brightness is higher when peroxide dose is increased from 20 kg to 30 kg/t in comparison to when the dose is increased from 30 kg to 40 kg/t. Further increases in peroxide dose may increase the brightness slightly. A single peroxide stage may increase the pulp brightness upto 10-12 points.

Table-2. Effect of chelation (Qstage) on metal content of soft wood kraft pulps

 A higher dose is required with mechanical pulps because of high concentration of chromophoric groups (2-4%) than chemical pulps (0.5 1.0%) in which pulps is already brightened with some other bleaching agents. The peroxide may be applied in a single stage or two stages; same dose applied in two stages develops higher pulp brightness. Two stages bleaching is performed with mechanical pulps or TCF pulps where as single peroxide stage is sufficient to enhance the brightness by 4-5 points. Results of the effect of peroxide dose on mechanical pulps is given in Fig.3.

Influence of pulping process on brightness development of spruce CMP.

Effect of temperature on the rate of bleaching of an oxygen delig-nified soft wood kraft pulp (kappa number 11 bleached with peroxide

Time and Temperature

The effect of temperature on the peroxide bleaching of TCF pulps are shown in Fig.4. Results show that increasing bleaching temperature improves the brightness of pulp Pressurised peroxide stage gives higher brightness than non pressurized bleaching at lower temperatures The maximum temperature is 130C above which cleavage of 0-0 bond in peroxide take place reducing bleaching ability of peroxide.

Effect of temperature on the rate of brightness development for a peroxide- bleached spruce TMP

Fig.4
The result sFig.5 indicate that brightness development is fast, reaching maximum in 30 minutes or less but the final brightness is less than achieved with the same chemical charge at lower temperature. The rapid decrease in brightness observed for higher temperature bleaching is the result of the peroxide being totally consumed. This occurs because at higher temperatures, the reaction rates of both the bleaching and decomposition reactions are increased. So at elevated temperatures good pretreatment, adequate liquor stabilization and relatively shorter retention time are important. A convenient rule of thumb guide for selecting proper bleaching conditions is shown in Fig. 6.

Relationship between time, temperature and alkalinity

pH
The pka for the formation of per hydroxyl anion is 11.6 at 25 oC. When H2 O2 is 50% dissociated pH and pka will be equal ([H2O2] = [OOH-]) when pH is 10.6, only 10% peroxide is dissociated. Since per hydroxyl anion is essential for brightness development, with the drop-in pH, brightness of the pulp also decreases (Fig.7).

Fig.7 Relatioship between final pH in an (EOP) stage and brightness in the bleaching of softwood kraft pulp (kappa no 29

 In peroxide bleaching stage alkalinity must be optimized to balance the formation of coloured compounds due to alkali darkening. Consistency has also an effect on the optimum alkalinity level. At medium consistency (9-12%) depending upon other process parameters molar ratio of caustic soda to hydrogen peroxide is 1:1. In high consistency (20-30%) bleaching, best results are obtained at sodium hydroxide to hydrogen peroxide molar ratio of 0.25. When short retention times are used, alkali charge must be increased to achieve the same brightness. However if temperature is increased, alkali charge must be decreased to obtain optimum bleaching results

Consistency
Increase in pulp consistency can lead to improved bleaching performance (Fig.8 & Fig.9). The wash press needed for operation of a high consistency bleach plant may provide an opportunity for the press filtrate to be recycled to recover the value of residue hydrogen peroxide.

Effect of pulp consistency on the brightness of an oxygen delignified softwood kraft pulp (kappa no 9) bleached in a pressurized peroxide stage

Effect of consistency on the brightness in the peroxide

bleaching of spruce groundwood

Raw Material
The brightness of a peroxide bleached pulp depends primarily on the structure of the residual lignin and lignin content of the pulp entering the peroxide stage i.e. brightness of the unbleached pulp. Bleaching of chemical pulps require lower peroxide charge to reach the same level of brightness as from a mechanical pulp. Higher the initial pulp brightness, higher will be the final brightness. Brightness of sulphite pulps is highest, followed by hardwood and softwood.

 For hardwood and softwood kraft pulps and for sulphite pulps the brightness obtained in a hydrogen peroxide stage is inversely proportional to the kappa number of incoming pulp. The relationship is linear and is independent of the delignification process used to produce pulp entering the bleaching stage. The benefit of low initial pulp kappa number on the final brightness of Table 1 gives the brightness of softwood TMP. The bleachability of mechanical pulps made from same wood species follows the trend GW>PGW > CT MP> TMP > RMP.

Effect of O-stage kappa number on the final brightness of an oxygen-delignified softwood kraft pulp (kappa no 6) bleached in an OQP sequence.

Unbleached brightness of softwood TMP

Carry Over
Carry over of the dissolved organic fragments usually increases the consumption of H2O2 The additional peroxide oxidizes the dissolved organics, reducing the colour of the effluent rather than increasing the brightness of the pulp by bleaching the lignin residues. In the conventional bleaching process, residual chlorine from the chlorination stage enters the following extraction stage and react with sodium hydroxide forming sodium hypochlorite. Both chlorine and hypochlorite consume part of hydrogen peroxide that otherwise would be available for pulp bleaching. Similar is the case with ClO2 Therefore an efficient washing stage between two stages is needed to minimize carryover of chlorine/chlorine dioxide

 In TCF bleaching the effectiveness of bleaching process depends upon efficiency of bleach plant washers. The performance of a P stage can be improved by minimizing the carryover from pulping process that contribute to chemical oxygen demand. P stage performance can also be improved by reducing the amount of dissolved lignin and metals (from recycled bleach plant effluent) that enters the P stage.

Metal Removal
Metal content of some typical wood species is given in Table 2. Some transition metal (manganese, copper, iron) catalyse the decomposition of hydrogen peroxide and contribute to the formation of hydroxyl radical HO., superoxide anion radical O-.2. The presence of low concentration of these radicals is necessary for hydrogen peroxide bleaching to proceed but high concentration of such radicals lead to poor selectivity and decreased bleaching.

Table-2 Typical metal ion content of wood species

 Alkaline earth (magnesium and calcium) compounds and sodium silicate appears to hinder hydrogen peroxide decomposition. These compounds may form complexes with transition metal ions, lowering their activity. Two approaches are being followed for reducing metal ion concentrations in pulp. Metal chelation at pH 4-7 followed by washing or liquor removal stage. Acid treatment stage at pH <3 followed by washing and treatment with magnesium salts to replenish the magnesium ions lost in the washing stage

 A chelation pretreatment step conducted at pH 4-7, for 30-60 minutes at 60-90 oC is shown to improve the brightness of pulp. Chelants used are sodium salts of ethylenediamine tetra acetic acid (EDTA) and diethylene triaminepenta acetic acid (DTPA). Table 3 shows typical metal profiles for pulps treated with EDTA. An acid wash stage is less selective than chelation in removing transition metal ions. The results in Fig.11 shows the significant removal of magnesium, calcium and manganese ions

Effect of acid treatment pH on the removal of metals from an oxygen delignified softwood kraft pulp

Effect of chelation (Q stage) on the metal content of softwood kraft pulps.

 In the peroxide stage, the metals bound to the pulp may be released and reduce the effectiveness of the bleaching reaction. The addition of 0.1 0.2% DTPA to the pulp may be required as a part of the P stage bleach liquor make up to tie up the released metal ions. DTPA is used often because it is more effective at higher pH than EDTA (Fig.12). The benefit of DTPA addition include a small brightness increase, higher hydrogen peroxide residual at the end of the bleach stage and tolerance for a wide alkalinity range. The effect of DTPA pretreatment on brightness development and peroxide consumption in the bleaching of spruce TMP is depicted in Fig.13.

Effect of DTPA addition in a Q stage on the final brightness of a softwood fraft pulp (kappa no 32.5) bleached in an OQP sequence

Effect of DTPA treatment on the brightness development and peroxide consumption in the bleaching of spruce CTMP

Magnesium Sulphate (Epson salt) and Sodium Silicate Addition

The non selective removal of metals in an acid wash stage produces a pulp that upon bleaching with hydrogen peroxide has a lower pulp brightness and viscosity. The peroxide residual is also lower as a result of the removal of magnesium ion in the acid wash step. Magnesium sulphate is reapplied to the pulp to restore the appropriate metal profile. Fig.14 shows several of the benefits that have been discussed.

Effects of chelant and magnesium addition on the brightness of an O2-delignified softwood kraft pulp (kappa no 8) bleached in sequences composed of ozone and peroxide stages

Addition of a chelation stage after the acidic ozone stage can lead to significant reduction in the hydrogen peroxide consumption (compare QZQP and QZP. The addition of magnesium sulphate to the P stage produces an even more dramatic improvement in both brightness and hydrogen peroxide consumption (compare QZP with and without magnesium sulphate addition). Both chelation and acid wash pretreatment are effective when provision is made to restore magnesium/manganese (Mg/Mn) balance.

 Studies have shown that Mg/Mn ratio of over 30 is needed for effective hydrogen peroxide bleaching under normal temperature conditions (<90oC) When hydrogen peroxide stage is performed at higher temperature (e.g. 120 oC) and under high pressure, the Mg/Mn ratio must be even higher > 100. In addition manganese levels must be less than 2 ppm to achieve the benefits of the accelerated pulp bleaching reactions

 Sodium silicate is an essential component of the bleaching liquor in the peroxide bleaching of chemithermo mechanical pulps (CTMP) Similar to magnesium, the silicate complexes the transition metals through oxygen or hydroxyl bridges Formation of complexes reduces catalytic activity of transition metals to decompose hydrogen peroxide

 The addition of 2% silicate in the high consistency P stage decreases the peroxide consumption to 91%, increase the brightness by 2 units (87.3 to 89.5) and improve pulp viscosity by 0.5 mPas. The benefits are in addition to those gained by using magnesium (0.5% on pulp). Sulphite mills are adding silicate but kraft mills are reluctant to add silicate to the bleaching process owing to the scale deposition on the process equipment. Effect of sodium silicate addition at different peroxide addition levels are show in Fig.15.

Effect of sodium silicate addition on brightness gain at different peroxide addition levels

Typical H2O2 Bleaching Sequences

Conventional:
Used as reinforcing chemical in the E stage of existing plant. It allow lower kappa factor to be used in chlorine/chlorine dioxide stages and giving lower bleach chemical consumption and lower AOX. It also allows the mills to enhance production capacity without increasing the capacity of existing chlorine dioxide plant. Charges are low and the performance expectations are modest. It also counteracts the alkali darkening. H2O2 is also applied in the final stage to replace NaOCl or to provide higher brightness and brightness stability in a short bleaching sequence.

Brightness gain obtained by addition of a final P stage to a CEHD sequence in the bleaching of a softwood kraft pulp

ECF
A typical ECF sequence used is DEOPDD. The conversion to ECF from conventional sequence to ECF is hampered by chlorine dioxide generating capacity, bleaching equipment capacity and configuration. Hydrogen peroxide reinforcement in the extraction stages allows many mills to maintain production capacity and pulp quality. Hydrogen peroxide can be used as a primary bleaching agent designed to reduce AOX formation by eliminating the first chlorine dioxide stage. Sequence such as QPDEPD can be used but the operating costs are high

TCF
Typical sequence like QPP can be implemented in the existing plant. The brightness obtained depends upon incoming pulp kappa number and effective metal management stages. This practice has been used by sulphite mills to obtain 90% ISO brightness pulps using less than 34% peroxide. Hydrogen peroxide also provides excellent brightness stability when peroxide is used at the end of the sequence that includes an ozone stage. Sequence like OZP, OZEP, OZEOPP and O (QZ) QPO can be used to produce acceptable market grade soft wood pulps provided strength degradation in the final peroxide stage is managed.

Pulp Quality Brightness Stability

Hydrogen peroxide is effective in eliminating carbonyl groups and a final P stage in the TCF sequences give excellent brightness stability even when bleached pulp has high residual lignin content. Fig.17 shows the comparative brightness stability reversion of pulps bleached in OZP and OPZ sequences after exposure to heat at 105oC. Using a peroxide stage in the conventional sequence C/D EOP DP gives excellent brightness stability. The drop in brightness is 1-2 points with peroxide as compared to 3-4 points without peroxide stage for a 90% ISO bleached pulp.

Thermal stability of an oxygen-delignified softwood kraft pulp (kappa no17.8) bleached in OQZP and OQPZ sequences

Pulp Strength
The strength properties of the conventional D or D/C EOPDEPD are not changed by the addition of hydrogen peroxide to the extraction stages. There are some reports suggesting a drop of 5-10% tear index at the same tensile index for TCF bleached to high brightness in comparison to oxygen delignified ECF pulps. Fig.18 shows the tear tensile relationship for MCC oxygen delignified softwood kraft pulp bleached to 90% ISO brightness in TCF (OAZQP) and ECF (ODEODD) sequences

Tear tensile relationship for an oxygen-delignified softwood kraft pulp bleached in ECF and TCf sequences

Cleanliness
Low kappa numbers required for achieving a high final brightness ensure low shive content in the incoming pulp. Pulp cleanliness is not an issue in TCF bleached mill However, hydrogen peroxide is not as effective as chlorine dioxide for bleaching shives and dirt. When hydrogen peroxide is used as reinforce oxidative extraction stage in an ECF sequence for the purpose of reducing kappa factor, conditions of the chlorine dioxide stage may be suitably adjusted to maintain pulp cleanliness. Some shive removal may take place in EOP stage but it is important to reduce pH in Dstage for shive control. The chlorine dioxide in the first stage may have to be increased to completely remove shives

Process Flow Sheets

Fig.19 refitting TCF sequences into existing bleach plants. The sequences were designed to maximize pulp, efficient use of residual H2O2 through counter current flow. Fig.20 TCF sequence using advanced non chlorine delignification technology and washing/pressing. Fig.21 pressurized H2O2 (PO) stage Figs.22-25 for mechanical pulps

Process flow sheets for TCF bleaching seque-nces suitable for refitting into existing bleach plants

Process flow sheet for a pressurized peroxide (PO) stage

Process flow sheet for a pressurized peroxide (PO) stage at 10% consistency

Flow sheet for a single stage, medium consistency, peroxide bleach plant

Flow sheet for a single stage high consistency bleach plant

Flow sheet for a two stage medium-high consistency bleach plant

Flow sheet for a two stage peroxidehydrosuphite bleaching process

 The addition points for hydrogen peroxide should be isolated from injection points of other chemicals such as sodium hydroxide or live steam. This is relevant for high temperature P stages. It is also crucial that hydrogen peroxide be mixed well with the pulp as inadequate mixing may result in hydrogen peroxide decomposition in pockets of extremely high alkalinity or temperature. Release of oxygen during decomposition can cause the pulp density in the P stage to be lower than normal and the towers may have to be operated at lower volume to prevent stock over flows. Brightness control in hydrogen peroxide bleaching stage may be difficult if the lignin content of the pulp varies over a wide range. Most processes can be controlled by maintaining a uniform low kappa number for the in-coming pulp.

Environmental Consideration
The effluent from peroxide stage is fully recyclable to recovery plant. This can reduce water consumption. TCF/ECF bleaching eliminates/reduces the formation of Dioxins and AOX. Hydrogen peroxide reinforced oxidative extraction stage can be used to reduce color of the mill effluent. The waste water from peroxide stage is much less toxic than C or D stage effluents and can be easily treated in the conventional effluent treatment plants

Hydrogen Peroxide Delignification

H2O2 destroys many of the chromophoric groups present in the pulp and those created by reagents applied in the previous stages. Cl2, ClO2 and O2 forms quinone groups. To eliminate such groups H2O2 is added in the alkaline extraction stage. At a temp. above 80C, H2O2 starts attacking lignin or oxygen bleached lignin. Use of peroxide at elevated temperatures reduces lignin content in unbleached pulps H2O2 can replace oxygen delignification but oxygen is more cost effective

 Several bleaching sequences including H2O2 delignification that have been proposed for commercial use are listed in Table-4. Three commercial processes used are shown in Figs.26-28. The first process is MINOX process (Fig.26). In this process, the peroxide stage is integrated into brown stock washing in a way similar to that for oxygen bleaching stage. Low charges of hydrogen peroxide and sodium hydroxide are used (less than 0.5%) which explains why delignification is limited to 20%.

Table-4 Bleaching sequences comprised of a hydrogen peroxide delignification stage

Flow sheet of the hydrogen peroxide delignification (MINOX) process

 The second process Lignox process (Fig.27) uses a Q stage followed by washing and peroxide stage. The hydrogen peroxide and sodium hydroxide charges are high (upto 3-4% on pulp for H2O2) and delignification can be as high as 50%. The oxygen stage and peroxide stage effluent can be integrated with brown stock washing but Q stage effluent because of high metal concentration is not integrated.

Flow sheet of the hydrogen peroxide delignification process following a metal complexing stage (LIGNOX process)

 The third process uses both oxygen and hydrogen peroxide to provide hydrogen peroxide reinforced oxygen delignification. Addition of low doses of H2O2 (0.2-0.5%) to conventional O stage, the delignification is extended. Because of lower alkali charge and temperature, the pulp viscosity is increased. A kappa number reduction of 60% is easily achieved. The scheme is shown in Fig.28. Non pressurized EO is possible. EOP stage can give 30-35% kappa number reduction when 0.5% H2O2 is applied. EOP is more attractive for sulphite pulps

Flow sheets of the combined Oxygen-hydrogen peroxide delignification process

Flow sheet of MC H2O2 delignification

Flow sheet of MC H2O2 + O2 delignification