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9.1 Characterization of Black Liquors 969

9.1.2

Physical Properties

The most important physical properties which affect evaporator and recovery boiler

design and operation include liquor viscosity, boiling point rise, surface tension,

density, thermal conductivity and heat capacity.

9.1.2.1 Viscosity

The viscosity of the black liquor is determined by its composition, the dry solids

content, and temperature. At low shear rates, black liquor behaves as a Newtonian

fluid, and the macromolecular components such as lignin and polysaccharide

molecules control the rheological properties. At a dry solids content of about 15%,

the viscosity of the black liquor is only three-fold that of water at a given temperature.

At about 50% solids content, however, black liquor behaves as a polymer

blend with water as plasticizer, and the viscosity increases exponentially with solids

content. The relationship between dry solids content and viscosity at a low

shear rate is expressed in Eq. (2) [8]:

Log

lbl

lw _ __

DS _ 373

T

0_679 _ 0_656 _ DS _ 373

T

_2_

where lbl is the viscosity of black liquor (in Pa.s); lw is the viscosity of water (in Pa.s):

DS is the weight fraction of dry solids in black liquor; and T is temperature (in K).

According to Eq. (2), viscosity can change by five orders of magnitude over the

range of dry solids contents typical for kraft black liquor recovery.

The shape of the dissolved lignin molecules is influenced by the content of residual

effective alkali of the black liquor. With decreasing pH, the volume occupied

by the lignin molecules increases. The larger spheres can entangle more easily,

and this contributes to a higher viscosity. Dissolved polysaccharides such as

xylan tend to form expanded random coils which greatly influence the viscosity of

black liquor. The viscosity of black liquor can be reduced by a heat treatment. The

black liquor is heated up to 180–190 °C to further degrade the polymeric material

in the presence of residual alkali. The resulting reduced viscosity allows the black

liquor to be concentrated up to 80% dry solids in order to maximize the benefits

of high dry solids in black liquor combustion [9].

9.1.2.2 Boiling Point Rise (BPR)

According to Raoult’s law, the vapor pressure of the solvent decreases proportionally

to themolal concentration of the solute. Thus, the boiling point of the black liquor

increases with increasing dry solids content. The BRP can increase up to values of

close to 30 °C for black liquors leaving the concentrator (BLS about 80%) [8]. The

dependency of BRP on dry solids content is illustrated graphically in Fig. 9.1[8].

970 9 Recovery

9.1 Characterization of Black Liquors

20 40 60 80

0

10

20

30

Boiling Point Rise [єC]

Solids Content [%]

Fig. 9.1 Boiling point rise (BPR) as a function of dry solids

content (according to Frederick [8]).

The inorganic compounds (sodium, potassium, etc.) constitute more than 90%

of the solute on a molar basis. Therefore, the BPR is mainly influenced by the salt

concentration in the black liquor. The BPR is an important parameter for evaluating

the efficiency of black liquor evaporators. Heat transfer is dependent upon the

temperature difference between the condensing steam and the evaporating black

liquor. More detailed information regarding the calculation of BPR as a function

of pressure and molal concentration are provided in Ref. [8].