Você está na página 1de 9

See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/223922833

Chemical composition and physical properties


of black liquors and their effects on liquor
recovery operation in Brazilian pulp mills
Article in Fuel April 2009
DOI: 10.1016/j.fuel.2008.10.016

CITATIONS

READS

44

2,603

3 authors, including:
Marcelo Cardoso
Federal University of Minas Gerais
20 PUBLICATIONS 119 CITATIONS
SEE PROFILE

All in-text references underlined in blue are linked to publications on ResearchGate,


letting you access and read them immediately.

Available from: M. L. Passos


Retrieved on: 29 September 2016

Fuel 88 (2009) 756763

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Chemical composition and physical properties of black liquors and their effects
on liquor recovery operation in Brazilian pulp mills
Marcelo Cardoso a,*, der Domingos de Oliveira a, Maria Laura Passos b
a
b

Department of Chemical Engineering/School of Engineering, Federal University of Minas Gerais (UFMG), Rua Esprito Santo, 356 Andar, 30160-030 Belo Horizonte, Brazil
Drying Center, Federal University of So Carlos (UFSCar), via Washington Luis, P.O. Box 676, 13565-905 So Carlos, Brazil

a r t i c l e

i n f o

Article history:
Received 16 May 2007
Received in revised form 12 September
2008
Accepted 7 October 2008
Available online 6 November 2008
Keywords:
Eucalyptus and bamboo black liquors
Chemical characterization
Physical properties
Rheology
Recovery unit

a b s t r a c t
Black liquor is the major by-product and fuel of pulp mills. In this work, effects of black liquor properties
on its recovery unit operation are analyzed. Thus, an experimental methodology for characterizing the
principal chemical and physical properties of eucalyptus Kraft and bamboo soda black liquors has been
developed, including sample collections from six Brazilian mills. Based on results, eucalyptus and bamboo 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
and the eucalyptus, the former has the lowest sulfur level, the highest silicon and lignin concentration
and, consequently, the highest apparent viscosity.
2008 Elsevier Ltd. All rights reserved.

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. However, in both processes, cellulose bers are disassociated from lignin by chemical reactions. These reactions occur in a pressurized
digester, where wood chips or bers are heated and cooked with
the cooking liquor, composed basically of NaOH (sodium hydroxide). Specically in the Kraft process, the sodium sulde (Na2S) is
added to the digester for improving the disassociation of lignin
from cellulose bers, 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 rst through a
set of multiple-effect evaporators, in which it is concentrated from
15% to about 7075% of solids to become an adequate fuel. Before
entering into the boiler, this liquor is generally mixed with the sodium sulfate to adjust the inorganic ion contents. The Kraft recovery 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
(.Domingos de Oliveira), merilau@task.com.br (M.L. Passos).
0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.10.016

ator. The molten inorganic salts produced (Na2S(l) and Na2CO3(l))


ow 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 claried and causticized to recycle 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 difcult to perform
[2].
The black liquor chemical composition depends on the type of
the raw material processed, i.e. softwoods (such as pine), hardwoods (such as eucalyptus) or brous plants (such as bamboo),
as well as, on the operational conditions of the pulping stage. However, 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 brous 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 recovery 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 brous plant bers, is a polymer formed by phenyl-propane structures. During
the pulping operation, the lignin is fragmented and the carbohydrates are dissolved and converted into acids of low molar mass;

M. Cardoso et al. / Fuel 88 (2009) 756763

757

Nomenclature
Css
Clig
D
HV
Mw
MMlig
O/I
T

solids concentration ()


lignin concentration ()
shear strain (s1)
heating value (kJ/kg)
mass molar (Da)
lignin mass molar (Da)
ratio of organic compound mass per inorganic compound mass ()
temperature (C)
apparent viscosity (cP)

Raw material (type of


wood or plant) and
pulping conditions
Black liquor physical
properties

Black liquor chemical


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. Simplied 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 behavior. From Fig. 3a, it is seen that liquors with high lignin and polysaccharide 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

qliquor
qliq
qss
s
ABNT
HPLC
NPE
GPC
TAPPI

liquor density (kg/m3)


liquid phase density (kg/m3)
solid phase density (kg/m3)
shear tension (mPa)
Brazilian association of technical norms
high-pressure liquid chromatography
non-processing elements
gel permeation chromatography
technical association of the pulp and paper industry

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 polysaccharide 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 spherical structures (Fig. 3b), which little affect the rheological liquor
behavior. At an intermediate pH (12.5 6 pH 6 11.5), there is a partial dissolution of lignin that associates in shapeless and voluminous chains (Fig. 3a), inuencing strongly the liquor viscosity. As
a consequence, the analysis of the black liquor ow behavior requires the correct identication 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, hazard 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 equipment walls, corroding these surfaces. Note that, at low liquor temperatures 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. However, 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-surfaces of heat exchange evaporators.
Furthermore, since brous plants contain a high silicon concentration [69], 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 difcult to perform.
In this work, the experimental methodology developed for characterizing the chemical composition and physical properties of
eucalyptus Kraft liquor [1,10] has been brought to date and also extended 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 predict 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) 756763

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

Physical characterization

Chemical composition
(elementary analysis)
Organic/inorganic ratio (O/I)
Lignin concentration (Clig)

Density (qliquor)

Lignin molar mass (MMlig)

Caloric heating value (heating value, HV)


Rheological behavior (apparent viscosity (g) as
function of temperature (T) solids concentration
(Css) and shear rate D)
Boiling point rise (BPR)

the liquor properties listed in Table 1 to identify the inuence 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 vulgaris 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%) liquors 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

concentrated eucalyptus liquor samples have been mixed together


at known proportions to achieve the solid concentration range required for performing the viscosity and density tests. Bamboo
weak liquor samples have been mixed, when necessary, with the
dried liquor powder (obtained from drying tests in the laboratory)
to reach the required solid concentration range.

2.2. Chemical characterization of black liquors


Methods employed for the liquor chemical characterization are
shown in Table 2. Results of these analyses supply data for predicting the liquor physical properties, especially its density and heating 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 determined by injecting samples into a CHN elementary analyzer (PerkinElmer, model 2400).
To analyze the organic to inorganic mass ratio (organic/inorganic ratio), the technical standard procedure T625 cm-85 is used
(Table 2). This consists in determining the amount of the sulfated-ash through the following steps: (a) heat liquor in a mufe
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)


Nitrogen (N)
Sodium (S)

Combustion of dried liquor in oxygen (>1000 C) Elementary Analyzer PerkinElmer, model CHN
2400 (based on thermal conductivity measurements)
Atomic absorption spectroscopy with addition of HCl

[1,10]

Potassium (K)

Atomic absorption spectroscopy

Sulfur (S)

Combustion of dried in oxygen under pressure following gravimetric sulfate determination by


BaSO4
Liquor oxidation under pressure following potentiometric titration with AgNO3

Chlorine (Cl)

Lignin

Silicon (Si)
Lignin concentration (Clig)
Molar mass (MMlig)

Organic/inorganic
materials

Organic to inorganic ratio


(O/I)

Colorimetry
Lignin precipitation methods
High pressure liquid chromatography with gel permeation columns using tetrahydrofurane as a
movable phase Shimadzu (GPC-802; GPC-803; GPC-802C)
Liquor combustion followed by dust analysis

TAPPI Test T266


om-94
TAPPI Test T266
om-94
ABNT Test MB
106/65
TAPPI Test T699
om-87
[2]
[1,10,11]
[1,10]
[1]

759

M. Cardoso et al. / Fuel 88 (2009) 756763

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 modied version 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 industrial plant, one of the six mills has been chosen arbitrarily to estimate 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 composition parameters in relation to its mean value (averaged over
one year and three months) have been calculated to analyze the actual 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 caloric, i.e. the heating value (HV) is evaluated using

TAPPI standard test T684 om-90. Following this method, a calorimetric 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 9893600/20). 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
uid, can be identied.
3. Results and discussion
Results of the elementary analysis for the eucalyptus and bamboo 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 element 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 molar mass, Clig and MMlig, and of the Kappa number are shown in Table 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 (identied by the standard deviation of each chemical composition 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)

Density

Liquor density at Css


(qliquor)
Heating value (HV)

Dry a known mass of liquor in oven at controlled temperature until mass constant Digital Metler
balance AB204 (104 g)
Pycnometry (mass and volume measurements) Digital Metler balance AB204 (104 g), heater plate
and standard 25 ml volumetric bottles
Heating by a complete oxidizing liquor in an adiabatic calorimetric bomb (Shimadzu model C-03)

TAPPI Test T650


om-89 [2]
[2,12]

Caloric
heating
value
Viscosity

Liquor apparent viscosity


at Css and T (g)

Viscosity measurements at different shear stresses and temperature Calibrated rotational Cole
Parmer viscometers, 98936-00 and -20 model with cylindrical spindles, adapters, unit of controlled
temperature

TAPPI Test T684


om-90 [2]
[2,12]

Table 4
Results from the elementary analysis of different black liquors.
Liquor (type of processed wood)

Mill location

Hardwood/Eucalyptus grandisa
Hardwood/E. grandisa
Hardwood/E. grandisa
Hardwood/E. grandisa
Hardwood/E. grandisa
Fibrous plant/Bambasa vulgarisa
Softwood/Pinus sylvestris and
Pinus caribaeab
Hardwoodb
Hardwood/Eucalyptusb
Fibrous plant/Strawc

Brazil/mill A (Kraft process)


Brazil/mill B (Kraft process)
Brazil/mill C (Kraft process)
Brazil/mill D (Kraft process)
Brazil/mill E (Kraft process)
Brazil/mill F (soda process)
Scandinavia and North America
(Kraft Process)
Scandinavia (Kraft process)
North America (Kraft process)
South America (soda process)

a
b
c

In this work.
In Ref. [14].
In Ref. [7].

Elementary composition (% mass per dry solids)


C

Na

Cl

Si

30.8
35.2
29.6
34.8
32.3 0.3
35.4
33.9 to 35.8

3.6
3.7
3.6
3.4
3.1 0.1
3.6
3.3 to 3.6

0.01

0.04
0.04 0.01
0.30
0.06 to 0.07

21.8
21.2
18.7
18.3
23.5 3.2
19.3
17.2 to 19.8

1.8
2.1
2.2
2.1
1.8 0.3
3.3
1.4 to 2.2

3.7
3.0
4.4
3.6
4.9 0.5
0.2
4.6 to 5.7

4.5
4.3
2.6
3.2
2.2 0.3
1.3
0.3 to 0.9

0.1

3.8

33.2
37.3
39.1

3.3
3.6
4.5

0.08
0.09
1.0

20.8
17.3
8.8

2.6
1.8
4.1

5.2
3.4
0.8

0.3
1.6
3.5

0.23

760

M. Cardoso et al. / Fuel 88 (2009) 756763

Table 5
Organic/inorganic ratio, concentration and lignin molar mass for black liquors coming from Kraft and soda processes.
Liquor (type/material processed)
a

Hardwood/Eucalyptus grandis
Hardwood/E. grandisa
Hardwood/E. grandisa
Hardwood/E. grandisa
Hardwood/E. grandisa
Fibrous plant/Bambosa vulgarisa
Softwood/Pinus Caribaeab
a
b

Mill location

Kappa number

O/I ()

Clig (%) (mass per mass dry solids)

MMlig (Da)

Brazil/mill A (Kraft process)


Brazil/mill B (Kraft process)
Brazil/mill C (Kraft process)
Brazil/Mill D (Kraft process)
Brazil/mill E (Kraft process)
Brazil/mill F (soda process)
Scandinavia (Kraft process)

17
17
17
17
17

17125

1.81
2.2
1.94
2.1
1.86 0.09
2.30
1.33

42.3
40.2
41.8
42.3
39.7 2.2
45.3
39.0

820
1641
1401
1050
1871 221
3282
2728

In this work.
In Ref. [15].

among the ve eucalyptus liquors analyzed. This means that the


usual oscillations occurred in the industrial process operation affect less signicantly 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 ve eucalyptus liquors analyzed here have their
own chemical composition.
As shown in Table 4, the bamboo black liquor contains the lowest sulfur content and highest silicon level. Both results are expected since there is no addition of Na2S in the soda process
(hydroxide ion is the only agent responsible for the lignin degradation) 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 composition. Therefore, serious operating problems should occur in the
recovery boiler because chloride and potassium ions tend to combine with the sodium ion to form a salt, which can build up on the
wall of recovery boiler tubes, plugging and corroding them (especially 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 specic Kraft mill must monitor and control these two ratio parameters to avoid problems with scaling.
Mean values of O/I and Clig obtained from Table 5 for the eucalyptus 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 number, 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], hardwoods delignify easier during pulping operation because its internal structure presents a larger number of open vessels, which
enhances the penetration and ow 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, promoting 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 efcacy of the
method developed for precipitating lignin from liquors, the absorption spectrum in the infrared region for each precipitated lignin obtained 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 eucalyptus liquor. The soda black liquor tend to have a high lignin molar
mass because of a lower degree of lignin dissociation in these liquors since, as mentioned earlier, the hydroxide ion is the only

Polystyrene standards
Lignin (Black liquor)

M.w 50000
M.w 30000

M.w 382000

M.w 17500
M.w 9000
M.w 2500

Toluen

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.

761

M. Cardoso et al. / Fuel 88 (2009) 756763

chemical responsible for it. Conversely, in the Kraft wood pulping,


hydroxide and hydrosulde ions act together to accelerate the lignin degradation and dissociation, reducing signicantly its molar
mass.
Based on data in Table 5, it is possible to conclude that, on average, MMlig is lower for eucalyptus liquors than it is for pine liquors.
This is explained by the faster delignication mechanism, characteristic 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 molar 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 specic concentration, inuences 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:

"

qliquor

C ss

qss

#1
1  C ss

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 t 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 tted by their curves obtained from Eq. (1).
As pointed out by Frederick [4], the variation of qliquor with Css is
strongly inuenced 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.
Mill/liquor

qss (kg/m3)

qliq (kg/m3)

Mill A/eucalyptus
Mill C/eucalyptus
Mill F/bamboo

1926 (258)
1936
2098

1005 (20)
1012
947

Table 7
Mean heating value (HV) of the eucalyptus and bamboo black liquors.
Mill/Liquor

HV (kJ/kg)

Mill A/eucalyptus
Mill E/eucalyptus
Mill F/bamboo

14593 (162)
14615 (268)
14673 (226)

Mill A
Mill C
Mill F - bamboo
Equation 1- mill A
Equation 1 - mill C
Equation 1 - mill F

1700
1500

eucalyptus liquor - mill E


pine liquor [21]

17000
16000

1300

HV (kJ/kg)

liquor (kg/m3)

compounds encountered in black liquor. Such statement is corroborated 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, specically for Kraft liquors (basically
pine liquors), Frederick [4] have suggested a linear relationship between 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 0.50 for both eucalyptus liquor and at
Css 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 bamboo (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 liquors. 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 liquor. 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 justies 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 liquor varies strongly with Clig, but insignicantly with O/I. Their
data are compared to HV data of the eucalyptus black liquor from

1100

15000
14000
13000
12000

900
0

20

40
Css (%)

60

80

Fig. 5. Liquor density (qliquor) as a function of the solids concentration (Css) for
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
correlation from Eq. (1): 12 kg/m3 for eucalyptus liquor from mill A, 5 kg/m3 for
eucalyptus liquor from mill C and 42 kg/m3 for bamboo liquor from mill F).

11000
0.7

0.9

1.1

1.3

1.5 1.7
O/I (-)

1.9

2.1

2.3

Fig. 6. Liquor heating value (HV) as function of the organic/inorganic ratio (O/I) for
the eucalyptus black liquor from mill E and the pine black liquor reported by Zaman
and Fricke [21].

762

M. Cardoso et al. / Fuel 88 (2009) 756763

eucalyptus liquor - mill E

1050
Css = 49.3% T= 35.3C
Css = 51.5% T= 37.2C
Css = 47,6% T= 37.3C
Css = 40.5% T= 31.5C

pine liquor [21]

17000

900
750

15000

(cP)

HV (kJ/kg)

16000

14000

600
450

13000

300

12000

150
0

11000
31

33

35

37
39
Clig (%)

41

43

45

Fig. 7. Liquor heating value (HV) as function of lignin concentration (Clig) for the
eucalyptus black liquor from mill E and the pine black liquor reported by Zaman
and Fricke [21].

15

20

Css = 35.9 % T = 29.5 C

50000

Css = 37.8 % T = 29.5 C


Css = 40.2 % T = 30.1 C

40000
(cP)

Css = 37.8 % T = 69.5 C

30000
20000
10000
0
0

10
shear rate (s-1)

15

20

Fig. 8. Liquor apparent viscosity, g, vs. shear rate, D, as function of Css and T: (a)
eucalyptus liquor from mill A and (b) bamboo liquor from mill F.

dent of shear rates (a constant of proportionality between the


shear stress (s) and the shear rate (D)). For Css > 40.5%, its reological
behavior is typical of a pseudoplastic uid, with g decreasing exponentially as the shear rate rises. As reported by Zaman and Fricke
[16], at the same range of temperature, the reological behavior of
the pine black liquor approaches to a Newtonian uid for Css 6 50%,
corroborating the effect of lignin concentration and mass molar on

220

(cP)

mill E, for varying O/I (Fig. 6) and for varying Clig (Fig. 7). Contrariwise, the HV of the eucalyptus black liquor depends explicitly on
O/I, but slightly on Clig. Both the organic components and the reduced sulfur compounds in black liquor contribute to its heating
values [4]. This non-expected result may indicate another organic
compound presented at a signicant concentration in the eucalyptus black liquor, affecting its heating value. Investigations about
the presence of other organic compounds in the liquor of eucalyptus and their inuence on the heating value, and also on the apparent viscosity, are currently being conducted. Additionally, It is
important to emphasize that the slash pine liquor, reported here,
has been obtained in the laboratory and its level of lignin differs
from the industrial liquor.
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
liquor viscosity is inuenced by its chemical composition, mainly
by the concentration of organic compounds, such as lignin and
polysaccharides [4].
As expected for both liquors, the lignin macromolecules entangle more easily at low shear rates increasing the black liquor viscosity. At high shear rates, these macromolecules tend to align
together reducing their resistance to ow and so the liquor
viscosity.
By comparing the rheological behavior of these two liquors, it is
conrmed that the apparent viscosity of the bamboo liquor is higher than one of the eucalyptus liquor, since the bamboo liquor has
the highest value of MMlig (Table 5). Furthermore, especially in
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
agglomerate with organic matter to form colloidal structures, as
pH is lowered. Such conditions can result in a high liquor apparent
viscosity even at low solids contents as shown in Fig. 8b. These
higher g values prevent an efcient evaporation of the bamboo liquor in multiple-effect evaporators and, consequently, a stable
combustion of this liquor in the furnace. Therefore, the recovery
of the bamboo liquor in the soda process requires the development
of new techniques to overcome problems related to its high viscosity. Passos et al. [22] have demonstrated that drying this liquor in a
low-cost spouted bed dryer to produce powdery fuel is a feasible
technique for recovering this liquor.
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 liquor approaches to a Newtonian uid, with its viscosity indepen-

10
shear rate (s-1)

200

increasing D

180

decreasing D

160
140
120
100
80
0

50

100
150
shear rate (s-1)

200

250

Fig. 9. Hysteresis occurred in eucalyptus black liquors for increasing and decreasing the shear rate (sample from mill A, Css = 52.0%, T = 30 C).

M. Cardoso et al. / Fuel 88 (2009) 756763

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
uids. Therefore, the black liquor of eucalyptus has the most complex 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 concentration (as expected in the soda pulping process), the highest silicon 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 inuences
physical and rheological properties of the eucalyptus and bamboo
liquors, imparting to them an own behavior in the industrial recovery evaporator and boiler different from the pine black liquor
behavior.
Acknowledgements
Authors are grateful to Brazilian governmental research foundations (FAPEMIG and CNPq) for the nancial support; to Brazilian
industries for supplying black liquor samples and to students
(S.C. Kupidlowski, C.R.S. Gonalves, A.O.S. Costa, R.M.S. Carmo,
A.L.G. Trindade, N.S. Oliveira, T.M.G. Ribeiro, D.C. Rena) for collecting data and performing tests.
References
[1] Cardoso M, Oliveira ED, Passos ML. Kraft black liquor of eucalyptus from
Brazilian mills: chemical and physical characteristics and its processing in the
recovery unit. O Papel 2006;67:7183.

763

[2] Trindade ALG. New technique to concentrate black liquors for producing
powdery fuel. M.Sc. Thesis. Belo Horizonte, UFMG: Federal University of Minas
Gerais; 2004 [in Portuguese].
[3] Soderhjelm L. Factors affecting the viscosity of strong black liquor. Appita J
1988;41:38992.
[4] Frederick WJ. In: Adams TN, Grace TM, Hupa M, Lisa K, Jones AK, Tran H,
editors. Kraft recovery boilers. New York: TAPPI Press; 1997 [chapter 3].
[5] Tran H. How does a recovery boiler become plugged? Kraft recovery
operations: Tappi short course notes. New York: TAPPI Press; 1990.
[6] Scurlock JMO, Dayton DC, Bamboo HB. An overlooked biomass resource?
Biomass Bioenerg 2000;19:22944.
[7] Gea G, Murillo MB, Arauzo J. Thermal degradation of alkaline black liquor from
straw: thermogravimetric study. Indust Engnr Chem Res 2002;41:471421.
[8] Myren BA. New approach to the non-wood black liquor problem. In: Pulping
conference, 2001, Seathe. Proceeding of non-wood panel. Seathe: TAPPI; 2001.
[9] Anselmo-Filho P, Badr O. Biomass resources for energy in North-Eastern Brazil.
Appl Energ 2004;77:5167.
[10] Cardoso M. Analysis of Eucalyptus black liquor recovery unit in the Kraft
process: evaluating alternative routes of processing. Ph.D. Thesis. UNICAMP:
State University of Campinas, Campinas; 1998 [in Portuguese].
[11] Kim H, Hill MK, Fricke AL. Preparation of kraft lignin from black liquor. Tappi J
1987;70:1126.
[12] Costa AOS, Passos ML, Cardoso, M. In: Comportamento reolgico do licor negro
de Eucalipto. 6 Jornada de engenharia qumica, UFU-UFMG, Uberlndia; 1999.
p. 5760.
[13] Costa GAA, Oliveira ED, Park SW, Cardoso M. Overall heat transfer coefcients
in a kraft black liquor industrial evaporation unit part I simulation of
multiple effect evaporation system. Appita J 2007;60:3216.
[14] Whitty K, Backman R, Forssn M, Hupa M, Rainio J, Sorvari V. Liquor to liquor
differences in combustion and gasication processes: pyrolysis behaviour and
char reactivity. J Pulp Paper Sci 1997;23:11927.
[15] Schmidl W, Dong DE, Fricke AL. Molecular weight and molecular weight
distribution of kraft lignins. Mat Res Soc Symp Proc 1990;197:2130.
[16] Zaman AA, Fricke AL. Steady shear ow properties of high solids softwood
Kraft black liquors: effect of temperature, solids concentrations, lignin
molecular weight and shear rate. Chem Eng Commun 1995;139:20123.
[17] MacDonald RG, eFranklin JN. The pulping of wood (pulp and paper
manufacture), 2nd ed., vol. 1. New York: McGraw-Hill; 1969.
[18] Britt KW. Handbook of pulp and paper technology. New York: Van Nostrand
Reinhold; 1964.
[19] Morais SAL. Contribution to the chemistry study of lignin from Eucalyptus
grandis. Ph.D. Thesis. UFMG: Federal University of Minas Gerais, Belo
Horizonte; 1987 [in Portuguese].
[20] Kupidlowski SC, Cardoso M, Passos, MLA, Carazza F. Characterization of
eucalyptus Kraft black liquor. In: Proceedings of the fth Brazilian symposium
on the chemistry of lignin and their wood components, Curitiba; 1997. p. 76
84.
[21] Zaman AA, Fricke AL. Effects of pulping conditions and black liquor
composition on the heat of combustion of slash pine black liquor. AICHE
Sympos Ser 1995;91:15461.
[22] Passos ML, Trindade ALG, dAngelo JVH, Cardoso M. Drying of black liquor in
spouted beds of inert particles. Dry Technol J 2004;22:104167.