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986 9 Recovery

Then the causticizing reaction transforms sodium carbonate from the smelt,

Na2CO3, to sodium hydroxide needed for cooking, thereby giving rise to calcium

carbonate, CaCO3:

Na2CO3 _ Ca_OH_2 _ 2NaOH _ CaCO3 DH≈ 0 kJ kmol_1 _13_

Calcium carbonate is separated from the white liquor and reburned at a temperature

above 820 °C following the endothermic calcination reaction:

CaCO3→CaO _ CO2 DH _ _178 kJ kmol_1 _14_

From a chemical perspective, white liquor is fundamentally characterized by

active or effective alkali concentration, by sulfidity, as well as by causticizing and

reduction efficiencies (see Section 4.2.2). In the causticizing plant, the total titratable

alkali (TTA) is also of interest. Causticizing efficiency, CE, and TTA are

defined as follows:

CE _

NaOH

NaOH _ Na2CO3 _ 100_ _15_

TTA _ NaOH _ Na2S _ Na2CO3 _16_

The concentrations of the sodium salts in Eqs. (15) and (16) are, by convention,

expressed in g L–1 and in terms of NaOH or Na2O equivalents.

Lime (CaO), calcium hydroxide (Ca(OH)2) and calcium carbonate (CaCO3), also

referred to as “lime mud”, all have a very low solubility in water. Reactions related

to these components are basically happening in the solid phase.

The equilibrium of the slaking reaction is far on the product side of Eq. (12),

and slaking is completed within 10–30 min. In contrast, the equilibrium of the

causticizing reaction in a typical kraft pulp mill would be reached at a causticizing

efficiency of about 85–90% (Fig. 9.11). The equilibrium conversion rate depends

mainly on total alkali, sulfidity, lime quality, and temperature. A higher TTA and

sulfidity reduce the equilibrium causticizing efficiency through product inhibition.

As the retention time proceeds, the causticizing reaction is increasingly limited

by the diffusion of reactants and reaction products through the increasingly

thicker layer of CaCO3 around the hydroxide core of the particle. The equilibrium

efficiency can be reached only with an excess of lime and at very long retention

times.

Actual mill operations deal with time restrictions, and must avoid over-liming

in order to maintain good filterability of the white liquor. As a consequence, the

average achievable causticizing efficiency on mill scale is 3–10% lower than the

equilibrium efficiency. Typical total retention times provided in the causticizers

are around 2.5 h.

9.2 Chemical Recovery Processes 987

40

60

80

100

120

140

160

180

200

70% 75% 80% 85% 90% 95% 100%

30

50

70

90

110

130

150

Total titrable alkali (TTA), g/L as NaOH

Causticising efficiency

Total titrable alkali (TTA), g/L as Na2O

Typical operation window

0% sulphidity

30% sulphidity

Fig. 9.11 Equilibrium causticizing efficiencies at 0% and 30%

sulfidity [14] and typical operating window for kraft mill causticizing

systems. Sulfidity in this diagram is defined as

NaOH/(Na2S + NaOH + Na2CO3).

9.2.3.2.3 White Liquor Preparation Processes and Equipment

The preparation of white liquor begins with smelt dissolving. Weak wash and

smelt form the green liquor, a solution of mainly sodium carbonate and sodium

sulfide. The green liquor carries some unburned carbon and insoluble inert material

from the smelt, which are detrimental to the downstream recovery and pulping

processes if not removed, together with lime mud particles. While the removal

of these so-called “dregs” was traditionally carried out by sedimentation, the

requirements of today’s increasingly closed mills are best met with green liquor

filtration. Since filters retain much smaller particles than clarifiers, the levels of