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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
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
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
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.
MoDo-CIL reactor
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
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.