Fuel 88 (2009) 756–763

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Fuel
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Chemical composition and physical properties of black liquors and their effects
on liquor recovery operation in Brazilian pulp mills
Marcelo Cardoso a,*, Éder Domingos de Oliveira a, Maria Laura Passos b
a
Department of Chemical Engineering/School of Engineering, Federal University of Minas Gerais (UFMG), Rua Espírito Santo, 35–6° Andar, 30160-030 Belo Horizonte, Brazil
b
Drying Center, Federal University of São Carlos (UFSCar), via Washington Luis, P.O. Box 676, 13565-905 São Carlos, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Black liquor is the major by-product and fuel of pulp mills. In this work, effects of black liquor properties
Received 16 May 2007 on its recovery unit operation are analyzed. Thus, an experimental methodology for characterizing the
Received in revised form 12 September principal chemical and physical properties of eucalyptus Kraft and bamboo soda black liquors has been
2008
developed, including sample collections from six Brazilian mills. Based on results, eucalyptus and bam-
Accepted 7 October 2008
Available online 6 November 2008
boo black liquors present higher contents of non-processing elements (NPEs), higher concentration and
different molar mass of lignin than those reported by the pine Kraft black liquor. This leads to distinct
rheological properties of these liquors. By comparing results obtained for the both liquors, the bamboo
Keywords:
Eucalyptus and bamboo black liquors
and the eucalyptus, the former has the lowest sulfur level, the highest silicon and lignin concentration
Chemical characterization and, consequently, the highest apparent viscosity.
Physical properties Ó 2008 Elsevier Ltd. All rights reserved.
Rheology
Recovery unit

1. Introduction
Kraft (or sulfate) and soda are the two major alkaline processes
to produce chemical pulps, being the former the most important
for pulp industries, while the latter is commonly applied to yield
non-wood pulps, such as bagasse, straw, grass and bamboo. How-
ever, in both processes, cellulose fibers are disassociated from lig-
nin by chemical reactions. These reactions occur in a pressurized
digester, where wood chips or fibers are heated and cooked with
the cooking liquor, composed basically of NaOH (sodium hydrox-
ide). Specifically in the Kraft process, the sodium sulfide (Na2S) is
added to the digester for improving the disassociation of lignin
from cellulose fibers, accelerating the wood cooking operation
and increasing the mechanical resistance of the pulp [1]. Note that
the products resulted from the digester reactions are the cellulose
pulp and the black liquor.
In the Kraft recovery unit, the black liquor passes first through a
set of multiple-effect evaporators, in which it is concentrated from
15% to about 70–75% of solids to become an adequate fuel. Before
entering into the boiler, this liquor is generally mixed with the so-
dium sulfate to adjust the inorganic ion contents. The Kraft recov-
ery boiler works as a chemical reactor (producing Na2S(l) and
Na2CO3(l)), as a steam generator (using the heat of combustion of
organic materials to produce vapor) and also as a residue inciner-
* Corresponding author. Tel./fax: +55 31 34091789.
E-mail addresses: mcardoso@deq.ufmg.br (M. Cardoso), eder@deq.ufmg.br
(É.Domingos de Oliveira), merilau@task.com.br (M.L. Passos).
ator. The molten inorganic salts produced (Na2S(l) and Na2CO3(l))
flow from the furnace (lower boiler region) to the dissolving tank,
in which they are mixed with the weak white liquor to generate
the green liquor. This green liquor is clarified and causticized to re-
cycle the calcium carbonate and to regenerate the white liquor,
which returns to the process [1]. Although, in the soda recovery
unit, the bamboo black liquor can be concentrated and burned,
its high viscosity limits the solid concentration up to 50%, witch
makes the bamboo black liquor recovery more difficult to perform
[2].
The black liquor chemical composition depends on the type of
the raw material processed, i.e. softwoods (such as pine), hard-
woods (such as eucalyptus) or fibrous plants (such as bamboo),
as well as, on the operational conditions of the pulping stage. How-
ever, for all raw materials and pulping operational conditions used,
the black liquor can be considered as a complex aqueous solution,
comprising organic materials from wood or fibrous plants (lignin,
polysaccharides and resinous compounds of a low molar mass)
and inorganic compounds (mainly soluble salt ions). Hence, as
summarized in Fig. 1, the black liquor chemical composition affects
its properties, basically those that govern its behavior in the recov-
ery unit [3].
Fig. 2 is a schematic diagram of the black liquor structure, which
comprises lignin and polysaccharide clusters, salt ions and water.
Note that, the lignin, the bonding agent of wood or fibrous plant fi-
bers, is a polymer formed by phenyl-propane structures. During
the pulping operation, the lignin is fragmented and the carbohy-
drates are dissolved and converted into acids of low molar mass;

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.10.016
 M. Cardoso et al. / Fuel 88 (2009) 756–763 757

Nomenclature

Css solids concentration () qliquor liquor density (kg/m3)

Clig lignin concentration () qliq liquid phase density (kg/m3)
D shear strain (s1) qss solid phase density (kg/m3)
HV heating value (kJ/kg) s shear tension (mPa)
Mw mass molar (Da) ABNT Brazilian association of technical norms
MMlig lignin mass molar (Da) HPLC high-pressure liquid chromatography
O/I ratio of organic compound mass per inorganic com- NPE non-processing elements
pound mass () GPC gel permeation chromatography
T temperature (°C) TAPPI technical association of the pulp and paper industry
g apparent viscosity (cP)

Raw material (type of
wood or plant) and
pulping conditions
Black liquor physical Black liquor chemical
properties composition
Black liquor behavior in
the recovery unit
(evaporators and boiler)
Fig. 1. Origin of the black liquor behavior in the industrial recovery unit (after
Soderhjelm [3]).
Fig. 2. Simplified schematic representation of the black liquor structure.
however, the fraction known as xylan (the main hemicellulose in
hardwoods) cannot be degraded. Therefore, this polysaccharide
survives from the pulping operation to compose the black liquor
[3].
As well known in the literature [1], the concentration, molar
mass and molecular conformation of lignin and polysaccharide,
presented in the black liquor, affect strongly its rheological behav-
ior. From Fig. 3a, it is seen that liquors with high lignin and poly-
saccharide concentrations tend to have a high viscosity, because
these two compounds can cluster into amorphous and voluminous
molecules of high molar mass. Conversely, as schematized in
Fig. 3b, liquors with low lignin and polysaccharide concentrations
tend to present a lower viscosity, since these compounds can
agglomerate in a more compact and spherical molecular structure
[1]. However, as reported by Frederick [4], the lignin and polysac-
charide macromolecule conformation is straightly related to the
pH environment. For pH > 12.5, phenol groups are ionized and
the lignin molecules become soluble, forming compact and spher-
ical structures (Fig. 3b), which little affect the rheological liquor
behavior. At an intermediate pH (12.5 6 pH 6 11.5), there is a par-
tial dissolution of lignin that associates in shapeless and volumi-
nous chains (Fig. 3a), influencing strongly the liquor viscosity. As
a consequence, the analysis of the black liquor flow behavior re-
quires the correct identification of its pH range.
In addition, the inert or non-processing elements (NPE) in black
liquors (as potassium, chlorine, calcium, aluminum, silicon and
iron ions) can also affect the liquor properties and, sometimes, haz-
ard the continuous operation of the industrial black liquor recovery
plant. As pointed out by Tran [5], the main operational problem
caused by the presence of these NPE is their incrustation on equip-
ment walls, corroding these surfaces. Note that, at low liquor tem-
peratures and solid concentrations (Css < 75%), aluminum, calcium
and silicon ions form, with the organic compounds, complexes that
can avoid building up an insoluble crust on evaporator walls. How-
ever, at high liquor temperatures and solid concentrations
(Css > 75%), these complexes, when formed, become destabilized,
releasing calcium, aluminum and silicon ions, which form calcium
carbonate and/or aluminum silicate, incrusting on the wall-sur-
faces of heat exchange evaporators.
Furthermore, since fibrous plants contain a high silicon concen-
tration [6–9], the bamboo liquor should present higher silicon ion
content. Thus, because the tendency of this ion to form and build
up insoluble complexes, the bamboo liquor recovery processing
should be more difficult to perform.
In this work, the experimental methodology developed for char-
acterizing the chemical composition and physical properties of
eucalyptus Kraft liquor [1,10] has been brought to date and also ex-
tended for characterizing the bamboo soda black liquor. Samples
have been collected from six Brazilian mills to characterize these
liquors. Results obtained have been analyzed to correlate the
chemical composition and the main physical properties of these
different types of black liquors, as well as, to identify the effects
of these parameters on the recovery operational variables and pre-
dict the liquor behavior in the industrial plant.
2. Experimental methodology
As shown in Table 1, the experimental methodology developed
consists in determining the elementary chemical composition of
these liquors and other important parameters that should affect
their physical properties. In parallel, this methodology evaluates
758 M. Cardoso et al. / Fuel 88 (2009) 756–763

Fig. 3. Schematic representation of lignin and polysaccharide conglomerates presented in black liquor: (a) voluminous and shapeless and (b) compact and spherical (after
Cardoso et al. [1]).

Table 1
Main parameters to be analyzed for black liquor characterization [1,10].
Chemical characterization
Chemical composition
(elementary analysis)
Organic/inorganic ratio (O/I)
Lignin concentration (Clig)
Lignin molar mass (MMlig)
concentrated eucalyptus liquor samples have been mixed together
at known proportions to achieve the solid concentration range re-
Physical characterization
quired for performing the viscosity and density tests. Bamboo
Density (qliquor)
weak liquor samples have been mixed, when necessary, with the
Calorific heating value (heating value, HV) dried liquor powder (obtained from drying tests in the laboratory)
Rheological behavior (apparent viscosity (g) as to reach the required solid concentration range.
function of temperature (T) solids concentration
(Css) and shear rate D)
Boiling point rise (BPR)
2.2. Chemical characterization of black liquors

the liquor properties listed in Table 1 to identify the influence of
chemical composition on them.
2.1. Sampling and storage
Five of the six Brazilian industries, selected in this work, use
Kraft process for producing cellulose pulp from Eucalyptus grandis
(hardwood basically). One used soda process from Bambasa vulga-
ris woody grasses. To characterize their black liquors, samples have
been taken from each industrial plant, from April 2000 to July
2005. In Kraft process mills, samples of weak (12% 6 Css 6 17%),
intermediate (38% 6 Css 6 44%) and strong (63% 6 Css 6 72%) li-
quors have been taken and stored at 4 °C. In the soda process mill,
only samples of weak liquors (14% 6 Css 6 16%) have been taken
and stored at 4 °C.
Prior to experiments, these samples have been equilibrated to
the room temperature. When necessary, two or three different
Methods employed for the liquor chemical characterization are
shown in Table 2. Results of these analyses supply data for predict-
ing the liquor physical properties, especially its density and heat-
ing value. The black liquor chemical composition is determined
using the elementary analysis technique. In this work, only the
compositions of the most important elements are presented, as
shown in Table 2. Such analyses have been performed according
to Technical Association of the Pulp and Paper Industry (TAPPI)
and Brazilian Association of Technical Norms (ABNT) standards.
Carbon, nitrogen and hydrogen (CHN) compositions are deter-
mined by injecting samples into a CHN elementary analyzer (Per-
kin–Elmer, model 2400).
To analyze the organic to inorganic mass ratio (organic/inor-
ganic ratio), the technical standard procedure T625 cm-85 is used
(Table 2). This consists in determining the amount of the sul-
fated-ash through the following steps: (a) heat liquor in a muffle
for drying; (b) add drops of concentrated sulfuric acid to the dry li-

Table 2
Techniques used in chemical characterization of eucalyptus and bamboo black liquors from Brazilian mills.

Analysis Measured parameters Technique and equipment used References

Elemental analysis Carbon (C) Hydrogen (H) Combustion of dried liquor in oxygen (>1000 °C) Elementary Analyzer Perkin–Elmer, model CHN [1,10]
Nitrogen (N) 2400 (based on thermal conductivity measurements)
Sodium (S) Atomic absorption spectroscopy with addition of HCl TAPPI Test T266
om-94
Potassium (K) Atomic absorption spectroscopy TAPPI Test T266
om-94
Sulfur (S) Combustion of dried in oxygen under pressure following gravimetric sulfate determination by ABNT Test MB
BaSO4 106/65
Chlorine (Cl) Liquor oxidation under pressure following potentiometric titration with AgNO3 TAPPI Test T699
om-87
Silicon (Si) Colorimetry [2]
Lignin Lignin concentration (Clig) Lignin precipitation methods [1,10,11]
Molar mass (MMlig) High pressure liquid chromatography with gel permeation columns using tetrahydrofurane as a [1,10]
movable phase – Shimadzu (GPC-802; GPC-803; GPC-802C)
Organic/inorganic Organic to inorganic ratio Liquor combustion followed by dust analysis [1]
materials (O/I)
 M. Cardoso et al. / Fuel 88 (2009) 756–763 759

quor [1] and (c) burn the organic matter by heating the liquor
excessively (T > 700 °C).
Data of lignin concentration (Clig) and its molar mass (MMlig) are
essential to describe changes in the rheological liquor behavior
during its evaporation. Before measuring these parameters, lignin
needs to precipitate from the black liquor. For this, a modified ver-
sion of the method proposed by Kim et al. [11] is used in this work
[10].
The high-pressure liquid chromatography technique (HPLC)
with gel permeation chromatography columns (GPC) is used to
determine MMlig (lignin molar mass). Tetrahydrofurane is selected
as the movable phase in this technique.
Since there are random oscillations in the operational variables
of the liquor recovery unit due to usual perturbations in the indus-
trial plant, one of the six mills has been chosen arbitrarily to esti-
mate the effect of these time oscillations on the liquor chemical
characterization. In this mill, the chemical composition of the black
liquor has been monitored during one year and three months of
operation and 56 liquor samples have been collected and analyzed.
Based on these data, the standard deviation of each chemical com-
position parameters in relation to its mean value (averaged over
one year and three months) have been calculated to analyze the ac-
tual data dispersion due to the usual oscillations and perturbations
occurred in the industrial process.
2.3. Physical characterization of black liquor
Methods used in the physical characterization of black liquor
are shown in Table 3. The solid concentration (Css) is obtained by
using the oven drying method at controlled temperature and the
density (qliquor) is determined by the pycnometric technique [2].
Black liquor calorific, i.e. the heating value (HV) is evaluated using
TAPPI standard test – T684 om-90. Following this method, a calo-
rimetric bomb (Shimadzu model C-03) has been used to determine
the heat of combustion of these black liquors at Css P 45%.
Tests for describing the rheological liquor behavior have been
carried out in a rotary rheometer (COLE-PARMER, models 98936-
00/20). Following methodology proposed by Costa et al. [12], s
(shear stress) vs. D (shear rate) curves are determined as a function
of Css and T (liquor temperature). Each experimental point on s vs.
D curves is averaged over two or three replications. These curves
are statistically analyzed to determine the apparent viscosity (g)
of eucalyptus and bamboo black liquors as the function of T and
Css [2,12,13]. Based on this s vs. D curves, the range of Css, at which
the liquor changes its behavior from Newtonian to pseudoplastic
fluid, can be identified.
3. Results and discussion
Results of the elementary analysis for the eucalyptus and bam-
boo black liquors are shown in Table 4. The composition of each
element (carbon, hydrogen, nitrogen, sodium, potassium, sulfur,
silicon and chlorine) expressed as the mass percentage of this ele-
ment to dry solids has been obtained from a series of (at least)
three tests, with a standard deviation lower than 1.5%. Data of
the organic/inorganic ratio, O/I, of the lignin concentration and mo-
lar mass, Clig and MMlig, and of the Kappa number are shown in Ta-
ble 5 for these liquors. For comparison, Tables 4 and 5 include also
data obtained from the literature [7,14,15].
Mill E is the one, in which the chemical composition of its liquor
has been monitored during one year and three months. As shown
in Tables 4 and 5, the chemical composition data dispersion of this
liquor (identified by the standard deviation of each chemical com-
position parameter) is lower than one of the chemical composition

Table 3
Techniques used in physical characterization of the eucalyptus and bamboo black liquors from Brazilian mills.

Analysis Measured parameters Technique and equipment used References

Solids contents Solids concentration (Css) Dry a known mass of liquor in oven at controlled temperature until mass constant – Digital Metler TAPPI Test T650
balance AB204 (±104 g) om-89 [2]
Density Liquor density at Css Pycnometry (mass and volume measurements) – Digital Metler balance AB204 (±104 g), heater plate [2,12]
(qliquor) and standard 25 ml volumetric bottles
Calorific Heating value (HV) Heating by a complete oxidizing liquor in an adiabatic calorimetric bomb (Shimadzu model C-03) TAPPI Test T684
heating om-90 [2]
value
Viscosity Liquor apparent viscosity Viscosity measurements at different shear stresses and temperature – Calibrated rotational Cole– [2,12]
at Css and T (g) Parmer viscometers, 98936-00 and -20 model with cylindrical spindles, adapters, unit of controlled
temperature

Table 4
Results from the elementary analysis of different black liquors.

Liquor (type of processed wood) Mill location Elementary composition (% mass per dry solids)
C H N Na K S Cl Si
Hardwood/Eucalyptus grandisa Brazil/mill A (Kraft process) 30.8 3.6 0.01 21.8 1.8 3.7 4.5 0.1
Hardwood/E. grandisa Brazil/mill B (Kraft process) 35.2 3.7 – 21.2 2.1 3.0 4.3 –
Hardwood/E. grandisa Brazil/mill C (Kraft process) 29.6 3.6 – 18.7 2.2 4.4 2.6 –
Hardwood/E. grandisa Brazil/mill D (Kraft process) 34.8 3.4 0.04 18.3 2.1 3.6 3.2 –
Hardwood/E. grandisa Brazil/mill E (Kraft process) 32.3 ± 0.3 3.1 ± 0.1 0.04 ± 0.01 23.5 ± 3.2 1.8 ± 0.3 4.9 ± 0.5 2.2 ± 0.3 –
Fibrous plant/Bambasa vulgarisa Brazil/mill F (soda process) 35.4 3.6 0.30 19.3 3.3 0.2 1.3 3.8
Softwood/Pinus sylvestris and Scandinavia and North America 33.9 to 35.8 3.3 to 3.6 0.06 to 0.07 17.2 to 19.8 1.4 to 2.2 4.6 to 5.7 0.3 to 0.9 –
Pinus caribaeab (Kraft Process)
Hardwoodb Scandinavia (Kraft process) 33.2 3.3 0.08 20.8 2.6 5.2 0.3 –
Hardwood/Eucalyptusb North America (Kraft process) 37.3 3.6 0.09 17.3 1.8 3.4 1.6 –
Fibrous plant/Strawc South America (soda process) 39.1 4.5 1.0 8.8 4.1 0.8 3.5 0.23
a
In this work.
b
In Ref. [14].
c
In Ref. [7].
760 M. Cardoso et al. / Fuel 88 (2009) 756–763

Table 5
Organic/inorganic ratio, concentration and lignin molar mass for black liquors coming from Kraft and soda processes.

Liquor (type/material processed) Mill location Kappa number O/I () Clig (%) (mass per mass dry solids) MMlig (Da)
a
Hardwood/Eucalyptus grandis Brazil/mill A (Kraft process) 17 1.81 42.3 820
Hardwood/E. grandisa Brazil/mill B (Kraft process) 17 2.2 40.2 1641
Hardwood/E. grandisa Brazil/mill C (Kraft process) 17 1.94 41.8 1401
Hardwood/E. grandisa Brazil/Mill D (Kraft process) 17 2.1 42.3 1050
Hardwood/E. grandisa Brazil/mill E (Kraft process) 17 1.86 ± 0.09 39.7 ± 2.2 1871 ± 221
Fibrous plant/Bambosa vulgarisa Brazil/mill F (soda process) – 2.30 45.3 3282
Softwood/Pinus Caribaeab Scandinavia (Kraft process) 17–125 1.33 39.0 2728
a
In this work.
b
In Ref. [15].

among the five eucalyptus liquors analyzed. This means that the
usual oscillations occurred in the industrial process operation af-
fect less significantly the liquor chemical composition. Therefore,
considering, as the experimental error, two times the standard
deviation of each parameter presented in Tables 4 and 5, one can
conclude that the five eucalyptus liquors analyzed here have their
own chemical composition.
As shown in Table 4, the bamboo black liquor contains the low-
est sulfur content and highest silicon level. Both results are ex-
pected since there is no addition of Na2S in the soda process
(hydroxide ion is the only agent responsible for the lignin degrada-
tion) and the bamboo itself has high silicon content in its
composition.
Data from Table 4 show also a high concentration of chlorine, a
non-processing element (NPE), in the Kraft eucalyptus liquor com-
position. Therefore, serious operating problems should occur in the
recovery boiler because chloride and potassium ions tend to com-
bine with the sodium ion to form a salt, which can build up on the
wall of recovery boiler tubes, plugging and corroding them (espe-
cially in super-heaters). In the boiler super-heater region, values
of Cl/(Na+ + K+) and K+/(Na+ + K+) ratios establish the adhesive
temperature range of this salt incrustation [5]. Therefore, each spe-
cific Kraft mill must monitor and control these two ratio parame-
ters to avoid problems with scaling.
Mean values of O/I and Clig obtained from Table 5 for the euca-
lyptus black liquor are, respectively 1.94 and 41.5%, higher than
those reported for the pine black liquor. This high organic matter
and lignin concentration in these eucalyptus black liquors can be
explained by the pulping process, expressed by a low Kappa num-
ber, and the internal wood structure. As known in the literature
[16], a low Kappa number is one of the hardwood pulp character-
istics, since these pulps have a small amount of residual lignin.
Such characteristic is corroborated by Kappa number data obtained
for eucalyptus liquors belonging to Brazilian mills, which are, in
average, lower than those reported for pine liquors (see Table 5).
According to MacDonald and Franklin [17] and Britt [18], hard-
woods delignify easier during pulping operation because its inter-
nal structure presents a larger number of open vessels, which
enhances the penetration and flow of the cooking liquor into the
wood chip. In softwoods, these vessels are resinous and obstructed,
hindering this mechanism of lignin removal. Besides, hardwoods
have a higher percentage of lignin in the medium lamella, promot-
ing its easy removal due to this outer location.
As shown in Fig. 4, for determining MMlig of eucalyptus liquors,
the permeation time of lignin, obtained in each liquor sample, has
to be compared to permeation time of each one of seven standard
polystyrenes with known molar masses (Mw = 2500, 5000, 9000,
17500, 30000, 50000 and 382000 Da). Using this procedure, MMlig
for each eucalyptus black liquor analyzed has been calculated and
its mean value is presented in Table 5. To verify the efficacy of the
method developed for precipitating lignin from liquors, the absorp-
tion spectrum in the infrared region for each precipitated lignin ob-
tained here has been compared to one for the lignin ‘‘in situ” of E.
grandis species, reported by Morais [19]. The similarity between
them corroborates that the precipitated material, obtained from
these liquors, is in fact lignin [10,20].
From Table 5, it can be inferred that values of O/I, Clig and MMlig
are higher for the bamboo liquor, meaning that this liquor contains
more lignin with larger structure molecular than does the eucalyp-
tus liquor. The soda black liquor tend to have a high lignin molar
mass because of a lower degree of lignin dissociation in these li-
quors since, as mentioned earlier, the hydroxide ion is the only

Polystyrene standards
Lignin (Black liquor)
M.w 50000
M.w 382000
M.w 30000
M.w 17500
M.w 9000
M.w 2500

Toluen

0 10 20 30 40 50 60
Time

Fig. 4. Typical chromatogram of the molar mass of lignin present in the eucalyptus black liquor of the sample coming from mill A with 73% of dry solids.
 M. Cardoso et al. / Fuel 88 (2009) 756–763 761

chemical responsible for it. Conversely, in the Kraft wood pulping,
hydroxide and hydrosulfide ions act together to accelerate the lig-
nin degradation and dissociation, reducing significantly its molar
mass.
Based on data in Table 5, it is possible to conclude that, on aver-
age, MMlig is lower for eucalyptus liquors than it is for pine liquors.
This is explained by the faster delignification mechanism, charac-
teristic of hardwoods, and also by the high sodium content in the
eucalyptus liquor. Zaman and Fricke [16] have pointed out the
alkalis present in white liquor aqueous solutions are responsible
for breaking macromolecules of lignin and, consequently, for
reducing MMlig of the liquor. Higher alkali contents are usually
indicated by the presence of higher tenors of sodium ions. Due to
these reasons, the Kraft eucalyptus liquor contains the lowest mo-
lar mass of lignin molecules among all black liquors.
The chemical composition of black liquor, basically the amount
of polymeric organic matter (lignin and polysaccharides) and of
inorganic compounds, as well as, their specific concentration, influ-
ences directly its physical properties, such as density (qliquor) and
viscosity (g). Results from earlier works [2,12] indicate that qliquor
varies with Css according to the following equation:
" #1
C ss ð1  C ss Þ
qliquor ¼ þ ð1Þ
qss qliq
where qss is the density of the solid phase and qliq is the density of
the liquid phase, both at the operating temperature. These densities,
qss and qliq, have been fit to experimental data and their values are
presented in Table 6 for eucalyptus liquors (mills A and C) and for
bamboo liquor (mill F). Fig. 5 shows the experimental data for these
three liquors fitted by their curves obtained from Eq. (1).
As pointed out by Frederick [4], the variation of qliquor with Css is
strongly influenced by the presence and concentration of inorganic
Table 6
Adjustable parameters of Eq. (1) to estimate the liquor density in the range of 26–
30 °C.
compounds encountered in black liquor. Such statement is corrob-
orated by data in Fig. 5 for eucalyptus black liquors from mills A
and C. Note that these two liquors present similar values of density
since their inorganic compositions are quite the same, as seen in
Tables 4 and 5. Furthermore, specifically for Kraft liquors (basically
pine liquors), Frederick [4] have suggested a linear relationship be-
tween qliquor and Css up to Css = 0.65. For 0.65 < Css < 0.80, changes
in qliquor with Css are more pronounced due to the liquor transition
from water-continuous phase to polymer-continuous phase. As
shown in the qliquor vs. Css curves of Fig. 5, there is, for these liquors,
a transition region after which qliquor rises faster with an increase
in Css. This occurs at Css ffi 0.50 for both eucalyptus liquor and at
Css ffi 0.40 for the bamboo liquor. Such result also corroborates
the effect of the amount of inorganic matter on the liquor density
since these bamboo and eucalyptus liquors have a quite distinct
inorganic composition (see Table 4).
The heating value (HV) of eucalyptus (mills A and E) and bam-
boo (mill F) liquors are presented in Table 7. Since HV of the lignin
extracted from hardwood is 25110 kJ/kg and lower than HV
(26900 kJ/kg) of the lignin extracted from softwood [4], one would
expect similar behavior for the HV of hardwood and softwood li-
quors. However, HV data in Table 7 are within the typical range
of the pine liquor HV, which is from 13400 to 15500 kJ/kg [4].
Returning to Table 5, one can see that Clig in the eucalyptus black
liquor is 39.7 to 42.3%, little higher than Clig (39%) in the pine li-
quor. This higher Clig counterbalances the lower HV of hardwood
lignin, resulting in the similar HV range for both, eucalyptus and
pine, liquors. This explanation also justifies HV data obtained for
the bamboo liquor, since HV of the lignin extracted from bamboo
is 24500 kJ/kg [9], lower than HV of the lignin extracted from both,
soft and hard, woods. Furthermore, Clig in the bamboo liquor is
45.3% (Table 5), higher than Clig in both, eucalyptus and pine,
liquors.
Zaman and Fricke [21] have reported that HV of slash pine li-
quor varies strongly with Clig, but insignificantly with O/I. Their
data are compared to HV data of the eucalyptus black liquor from

Mill/liquor qss (kg/m3) qliq (kg/m3) Table 7

Mean heating value (HV) of the eucalyptus and bamboo black liquors.
Mill A/eucalyptus 1926 (±258) 1005 (±20)
Mill C/eucalyptus 1936 1012 Mill/Liquor HV (kJ/kg)
Mill F/bamboo 2098 947
Mill A/eucalyptus 14593 (±162)
Mill E/eucalyptus 14615 (±268)
Mill F/bamboo 14673 (±226)

1700 Mill A
Mill C
Mill F - bamboo
Equation 1- mill A eucalyptus liquor - mill E
17000
1500 Equation 1 - mill C pine liquor [21]
ρliquor (kg/m3)

Equation 1 - mill F
16000

1300 15000
HV (kJ/kg)

14000
1100
13000

900 12000
0 20 40 60 80
11000
Css (%)
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3
Fig. 5. Liquor density (qliquor) as a function of the solids concentration (Css) for O/I (-)
eucalyptus black liquors from mill A and C and for bamboo black liquor from mill F
at temperature between 26 to 30 °C. (density error between experimental data and Fig. 6. Liquor heating value (HV) as function of the organic/inorganic ratio (O/I) for
correlation from Eq. (1): ±12 kg/m3 for eucalyptus liquor from mill A, ±5 kg/m3 for the eucalyptus black liquor from mill E and the pine black liquor reported by Zaman
eucalyptus liquor from mill C and ±42 kg/m3 for bamboo liquor from mill F). and Fricke [21].
762 M. Cardoso et al. / Fuel 88 (2009) 756–763

eucalyptus liquor - mill E a 1050

17000 pine liquor [21] Css = 49.3% T= 35.3˚C
900 Css = 51.5% T= 37.2˚C
16000 Css = 47,6% T= 37.3ºC
750 Css = 40.5% T= 31.5˚C
15000
HV (kJ/kg)

600

η (cP)
14000 450
13000 300

12000 150

11000 0
31 33 35 37 39 41 43 45 0 5 10 15 20
Clig (%) shear rate (s-1)

Fig. 7. Liquor heating value (HV) as function of lignin concentration (Clig) for the b Css = 35.9 % T = 29.5 ˚C
eucalyptus black liquor from mill E and the pine black liquor reported by Zaman 50000
and Fricke [21]. Css = 37.8 % T = 29.5 ˚C

40000 Css = 40.2 % T = 30.1 ˚C

Css = 37.8 % T = 69.5 ˚C
mill E, for varying O/I (Fig. 6) and for varying Clig (Fig. 7). Contrari-
wise, the HV of the eucalyptus black liquor depends explicitly on η (cP) 30000
O/I, but slightly on Clig. Both the organic components and the re-
duced sulfur compounds in black liquor contribute to its heating 20000
values [4]. This non-expected result may indicate another organic
compound presented at a significant concentration in the eucalyp-
10000
tus black liquor, affecting its heating value. Investigations about
the presence of other organic compounds in the liquor of eucalyp-
tus and their influence on the heating value, and also on the appar- 0
ent viscosity, are currently being conducted. Additionally, It is
0 5 10 15 20
important to emphasize that the slash pine liquor, reported here, shear rate (s-1)
has been obtained in the laboratory and its level of lignin differs Fig. 8. Liquor apparent viscosity, g, vs. shear rate, D, as function of Css and T: (a)
from the industrial liquor. eucalyptus liquor from mill A and (b) bamboo liquor from mill F.
The apparent viscosity (g) of eucalyptus and bamboo liquors as
function of the shear strain (D) is shown in Fig. 8, for different solid
concentrations (Css) and liquor temperature (T). The apparent black dent of shear rates (a constant of proportionality between the
liquor viscosity is influenced by its chemical composition, mainly shear stress (s) and the shear rate (D)). For Css > 40.5%, its reological
by the concentration of organic compounds, such as lignin and behavior is typical of a pseudoplastic fluid, with g decreasing expo-
polysaccharides [4]. nentially as the shear rate rises. As reported by Zaman and Fricke
As expected for both liquors, the lignin macromolecules entan- [16], at the same range of temperature, the reological behavior of
gle more easily at low shear rates increasing the black liquor vis- the pine black liquor approaches to a Newtonian fluid for Css 6 50%,
cosity. At high shear rates, these macromolecules tend to align corroborating the effect of lignin concentration and mass molar on
together reducing their resistance to flow and so the liquor
viscosity.
By comparing the rheological behavior of these two liquors, it is
confirmed that the apparent viscosity of the bamboo liquor is high- 220
er than one of the eucalyptus liquor, since the bamboo liquor has
the highest value of MMlig (Table 5). Furthermore, especially in 200 increasing D
non-wood soda bamboo liquor, a high silicon level exists, as shown
in Table 4, in the form of water-soluble silicate ions. These ions 180 decreasing D
agglomerate with organic matter to form colloidal structures, as
pH is lowered. Such conditions can result in a high liquor apparent 160
η (cP)

viscosity even at low solids contents as shown in Fig. 8b. These

higher g values prevent an efficient evaporation of the bamboo li-
140
quor in multiple-effect evaporators and, consequently, a stable
120
combustion of this liquor in the furnace. Therefore, the recovery
of the bamboo liquor in the soda process requires the development 100
of new techniques to overcome problems related to its high viscos-
ity. Passos et al. [22] have demonstrated that drying this liquor in a 80
low-cost spouted bed dryer to produce powdery fuel is a feasible 0 50 100 150 200 250
technique for recovering this liquor.
shear rate (s-1)
Based on Fig. 8a, one can see that, for Css 6 40.5% at
30 °C 6 T 6 40 °C, the reological behavior of eucalyptus black li- Fig. 9. Hysteresis occurred in eucalyptus black liquors for increasing and decreas-
quor approaches to a Newtonian fluid, with its viscosity indepen- ing the shear rate (sample from mill A, Css = 52.0%, T = 30 °C).
 M. Cardoso et al. / Fuel 88 (2009) 756–763
the liquor viscosity. Although the bamboo liquor presents a similar
behavior (see Fig. 8b), its pseudoplastic behavior occurs at lower
solid concentrations (Css < 35% at 29 °C 6 T 6 30 °C).
In addition, the hysteresis, observed in Fig. 9 for the eucalyptus
liquor, is not seen in bamboo and pine liquor rheological curves.
This hysteresis phenomenon occurs in thixotropic pseudoplastic
fluids. Therefore, the black liquor of eucalyptus has the most com-
plex rheological behavior.
4. Conclusion
Results show that the eucalyptus black liquor from Brazilian
mills presents a higher content of non-processing elements (NPEs),
a higher lignin concentration and a lower lignin molar mass than
the pine liquor from northern Hemisphere mills does. On the other
hand, the bamboo black liquor presents the lowest sulfur concen-
tration (as expected in the soda pulping process), the highest sili-
con and lignin concentrations and the highest lignin molar mass
in relation to the pine and eucalyptus liquors. This confers to this
liquor the highest apparent viscosity. From these results, it is
shown in this work how the chemical composition influences
physical and rheological properties of the eucalyptus and bamboo
liquors, imparting to them an own behavior in the industrial recov-
ery evaporator and boiler — different from the pine black liquor
behavior.
Acknowledgements
Authors are grateful to Brazilian governmental research founda-
tions (FAPEMIG and CNPq) for the financial support; to Brazilian
industries for supplying black liquor samples and to students
(S.C. Kupidlowski, C.R.S. Gonçalves, A.O.S. Costa, R.M.S. Carmo,
A.L.G. Trindade, N.S. Oliveira, T.M.G. Ribeiro, D.C. Rena) for collect-
ing data and performing tests.
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