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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
757
Nomenclature
Css
Clig
D
HV
Mw
MMlig
O/I
T
qliquor
qliq
qss
s
ABNT
HPLC
NPE
GPC
TAPPI
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
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)
Table 2
Techniques used in chemical characterization of eucalyptus and bamboo black liquors from Brazilian mills.
Analysis
Measured parameters
References
Elemental analysis
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)
Sulfur (S)
Chlorine (Cl)
Lignin
Silicon (Si)
Lignin concentration (Clig)
Molar mass (MMlig)
Organic/inorganic
materials
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
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 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
References
Solids contents
Density
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)
Caloric
heating
value
Viscosity
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
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
a
b
c
In this work.
In Ref. [14].
In Ref. [7].
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
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 ()
MMlig (Da)
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].
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
"
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
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
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
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
50000
40000
(cP)
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.
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).
763
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