ECF Bleaching

ECF means Elemental Chlorine Free bleaching Elemental chlorine is considered to be C and H Use of chlorine is still primarily because of low cost. Disadvantages on quality and environmental front. One of the foremost is the extensive pulp degradation particularly in the H stage The other is high environmental loads particularly chloroorganics responsible for the effluent toxicity represented by AOX and effluent color and high color reversion tendency of bleached papers one can achieve moderate brightness of 78-82 % depending upon raw material & pulping process For many end applications particularly printing grades high brightness pulps are required

 Modern bleaching processes are Elemental Chlorine Free (ECF) and Total Chlorine Free (TCF) bleaching processes. ECF process employ elemental chlorine free (C & H stages) bleach chemicals like chlorine dioxide (D) and non chlorine bleaching chemicals like oxygen, hydrogen peroxide, enzymes, per acids etc. In TCF processes ozone and non chlorine chemicals as used in ECF are employed. ECF and TCF pulping processes differ mainly on two fronts- pulp strength and environmental loads. ECF bleached pulps are stronger than TCF pulps. TCF processes give very low AOX values and the effluent is easily treatable and recyclable

Oxygen delignification/ pre-bleaching

It involves the use of molecular oxygen in alkaline media at elevated temperatures and under pressure. Biggest advantage of oxygen delignification (O) is that lignin content can be reduced by 40-50 %. Bleach chemical demand in subsequent bleaching stages drops by up to 50 %, reducing formation of chloroorganics (AOX) effluent color, BOD and COD Oxygen stage effluent can be used for washing of unbleached pulp effuent reaches chemical recovery, alkali and additional steam becomes available from organics present in waste waters Thus no pollution comes from Oxygen stage Selectivity good and pulp easily bleached to +90% Bleaching cost low - lower chemical consumption oxygen stage an integral part of pulp bleaching

Chemistry Oxygen is an unusual molecule It contains two unpaired electrons and is considered as free di radical It is less reactive than other free radicals but can attack appropriate substrates at regions of high electron density

Stepwise reduction of oxygen

Steps in mechanism of oxygen bleaching

 It involves the formation of per hydroxyl anion, hydrogen peroxide and free radicals like hydroxyl radical OH., hydro trioxy radical HOOO. and singlet oxygen O2. Complex oxidation processes that occur in oxygen bleaching include radical chain reactions involving organic species from both lignin and carbohydrates The following figure shows the likely initiation, propagation and termination steps Substrate is activated under alkaline conditions by ionizing the free phenolics groups present in residual lignin Resultant anion is electron rich and vulnerable to attack oxygen An added complication and of great significance is the involvement of trace quantities of transition metals acting as catalysts for peroxide decomposition. This decomposition forms hydroxyl radical with poor selectivity is responsible for attack on cellulose giving pulp degradation

Initial reactions leading to oxygen delignification

Reactions of intermediate hydroperoxides

Reactions of hydroperoxide intermediates to form muconic acids and quinnones

Oxidation and cleavage of cellulose chains

Carbohydrate reactions not leading to chain cleavage

Effect of addition of magnesium ion on selectivity

Magnesium Sulphate hepta hydrate Epsom salt is normally applied at 0.05-0.1% Mg 2+ on OD pulp. It is believed to function by precipitating magnesium hydroxide which adsorbs metal ions or making them unavailable for catalysis of peroxide decomposition It is apparent from the curve that selectivity do not remain constant as the kappa number of the pulp is decreased. However the selectivity remains constant until about 50% of the lignin is removed

Effect of black liquor carryover and dissolved solids recirculation on oxygen stage selectivity at 25% consistency

Carry over of the black liquor from the brown stock washers in to oxygen stage adversely affects selectivity

 Treatment of unbleached pulp with nitrogen peroxide (Prenox process) in the presence of oxygen makes the oxygen stage more selective and efficient even when the oxygen conditions are mild Lignin removal in oxygen stage can be as high as 80% considerably enhancing pollution abatement benefits Two types of commercial processes have been developed and are in commercial operation These are Medium Consistency (MC) and High Consistency (HC) processes HC processes are the earlier processes, MC processes are recent addition Now a days all newer units installed are exclusively MC processes.

Operating data of oxygen delignification

Flow sheet of MC oxygen delignification

Flow sheet of high consistency oxygen delignification

MoDo-CIL reactor

Bottom section of HC reactor used for Sapoxal Process

 The change over to MC units is due to lower capital cost, greater ease of handling and mixing and pumping technology, improved selectivity in presence of appreciable amounts of black liquor solids. However the chemical consumption is higher in MC than HC oxygen delignification

Effect of temperature on oxygen delignification rate

Effect of time, alkali charge and consistency on kappa number

Effect of time, alkali charge and consistency on viscosity

 The general trend is to optimize the various parameters so as to achieve 4050% reduction in pulp kappa number. Adjustment of alkali charge to target desired kappa reduction is practiced for routine adjustments.