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In the black liquor, from water formed out of hydrogen in organic material, and

from sootblowing steam. Increasing the dry solids concentration of the black

liquor, and thereby reducing the water input to the boiler, leads to a higher steam

generation per mass unit of black liquor solids (Fig. 9.9).

984

9.2 Chemical Recovery Processes

Tab. 9.4 Simplified recovery boiler heat balance.

System input/output Mass

[kg ton–1 dry solids]

Specific enthalpy

[kJ kg–1]

Enthalpy

[MJ ton–1 dry solids]

Enthalpy of input/output streams

Black liquor 1.333 2.8 . 130 485

Pre-heated air (dry) 4.909 1.0 . 120 589

Humidity of pre-heated air 70 2.725 190

Sootblowing steam 100 2.820 282

Flue gas (dry) 5.137 0.96 . 180 –888

Humidity of flue gas 827 2.840 –2.349

Smelt 448 1.500 –672

Reaction enthalpy

HHVof black liquor solids 1.000 14.000 14.000

Reduction to Na2S 89 13.090 –1.170

Reduction to K2S 25 9.625 –244

Losses –300

Heat to steam 9.923

Feedwater/steam

Feedwater 3.494 510 1.782

Total steam generation 3.494 3.350 11.705

90%

95%

100%

105%

110%

60% 70% 80% 90%

Relative steam generation

Black liquor solids concentration, wt.-%

Fig. 9.9 Steam generation in a recovery boiler as a function of

the black liquor solids concentration; typical curve normalized

to 100% at 75% solids concentration.

985

9.2.3.2 Causticizing and Lime Reburning

9.2.3.2.1 Overview

The causticizing and lime reburning operations target at the efficient conversion

of sodium carbonate from the smelt to sodium hydroxide needed for cooking. As

a part of the cooking chemical cycle, the preparation of white liquor consists of

several process steps, and is accompanied by a separate chemical loop, the lime

cycle (Fig. 9.10). The generated white liquor ought to contain a minimum of residual

sodium carbonate in order to maintain the dead solids load in the cooking

chemical cycle as low as possible.

Cooking /

washing

COOKING

CHEMICAL

CYCLE

Evaporation

Recovery

boiler

Smelt

dissolving

Green liquor

filtration /

Slaking clarification

Causticising

Whilte liquor

filtration

LIME

CYCLE

Lime reburning

Lime mud

washing

Fig. 9.10 Major unit operations of causticizing and lime

reburning in the context of the kraft chemical recovery cycle.

Process wise, the smelt coming from the smelt spouts of the recovery boiler

drops into the smelt dissolving tank and becomes dissolved in weak wash, thereby

forming green liquor. Since the smelt carries impurities which disturb the subsequent

process steps, those must be removed by clarification or filtration of the

green liquor. Then follow slaking, causticizing and white liquor filtration. After

separation from the white liquor, the lime is washed and reburned for re-use in

causticizing.

9.2.3.2.2 Chemistry

The basic chemical reactions in the causticizing plant and lime kiln start with the

exothermic slaking reaction, where burned lime, CaO, is converted into calcium

hydroxide, Ca(OH)2 (slaked lime):

CaO _ H2O→Ca_OH_2 DH _ _65 kJ kmol_1 _12_