Causticizing

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Overliming

Sunday, July 22nd, 2007

The critical factor in the operation of pressure filters is the quality of feed. Dregs and overliming cause blinding of the white liquor filter media, requiring more frequent acid washes. Overliming happens when the molar ratio of CaO/Na2CO3 is larger than that required to reach the equilibrium causticity, for a given ionic strength of the liquor (CaO+ Na2CO3+H2O?2NaOH+CaCO3). However, in actual mill practice, problems associated with overliming tend to occur when the molar ratio is 3-5% below the equilibrium causticity. Improved green liquor clarification and good control at the slaker are required to prevent problems in filters.  Mills may increase the use of fresh lime due to poor control, or in order to increase causticizing efficiency. To improve causticizing efficiency without adding excess lime, advanced causticizing control or partial borate autocaustcizing is recommended.   Poor settling of lime mud is attributed to a surge of fresh lime added as make-up. The fresh lime make-up should be added on a steady basis, dependent on the losses experienced by the system. The quality of the purchased lime is also important. The slaking reaction (CaO+H2OàCa(OH)2) generates a lot of heat, and proceeds quickly with a maximum temperature rise in 2-8 minutes, depending on the type of reburned lime*.  Reburned lime with a longer slaking time always has better settling and filtering properties than fresh lime. Research has shown that reburned lime is an agglomeration of small CaO crystals, with large voids between the crystals. Since slaking and causticizing reactions take place on the surface of solid particles, the reaction rates depend on the available surface and are inversely related to the degree of agglomeration due to sintering. This indicates that producing a kiln product with a high degree of sintering is desirable for optimum results in causticizing.  * C.F. Cornell, Current recausticizing practice, Part 2-Principles, 1996 Tappi Kraft recovery short course



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Solubility problems in green liquor processing

Saturday, March 3rd, 2007

Pirssonite, a double salt of sodium and calcium carbonate (Na2CO3.CaCO3.2H2O) often deposits in smelt dissolving tanks, green liquor lines, clarifiers and storage tanks; the scale has a stratified appearance. The scaling tendency depends on the concentration of total titratable alkali (TTA) in the green liquor, the liquor temperature, the calcium concentration, and the efficiency of mixing in the dissolving tank. Pirssonite forms at temperatures above 35 C in solutions containing high concentrations of Na2CO3, other sodium salts and calcium (i.e., CaCO3). The solubility of pirssonite decreases as the NaOH concentration increases. Other sodium salts have the same effect as NaOH. The solubility also decreases as green liquor cools. The change in Na2CO3 solubility is about 0.5 lb/ft3 (8 g/L) as Na2O per 10 C change in temperature*.

Pirssonite solubility curves (Na2CO3 concentration versus other Na salts concentration) are available at different temperatures. These curves can be used to determine the maximum TTA level at which the pirssonite will precipitate in green liquor (TTA sat). This level will vary from mill to mill because of differences in the composition of the green liquors. To find out the TTA sat, the mill operating line has to be defined. The intersection of this line with the solubility curves determines the upper limit for green liquor concentration. It is recommended that the operating TTA max should be 5-10% below TTA sat.

* Frederick, Jr., W.J. et al, “Pirssonite Deposits in Green Liquor Processing”, Tappi J., 73(2): 135-140, 1990.



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