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Fuel 88 (2009) 756–763

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Fuel journal homepage: www.else vier.com/locate/fuel Chemical composition and physical properties of black

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

article info

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

abstract

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 bam- 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 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. 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 (Na 2 S) 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 Na 2 S ( l ) and Na 2 CO 3( 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).

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 (Na 2 S ( l ) and Na 2 CO 3( 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;

M. Cardoso et al. / Fuel 88 (2009) 756–763

757

Nomenclature solids concentration ( ) lignin concentration ( ) q C ss liquor q C
Nomenclature
solids concentration ( )
lignin concentration ( )
q
C ss
liquor
q
C lig
liq
D
shear strain (s 1 )
heating value (kJ/kg)
mass molar (Da)
lignin mass molar (Da)
ratio of organic compound mass per inorganic com-
pound mass ( )
q
liquor density (kg/m 3 )
liquid phase density (kg/m 3 )
solid phase density (kg/m 3 )
ss
HV
s
M w
ABNT
HPLC
MM lig
O/I
NPE
GPC
T temperature ( C)
TAPPI
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
g apparent viscosity (cP)

Raw material (type of wood or plant) and pulping conditions

Raw material (type of wood or plant) and pulping conditions Black liquor physical properties Black liquor
Raw material (type of wood or plant) and pulping conditions Black liquor physical properties Black liquor

Black liquor physical properties

Black liquor chemical composition

liquor physical properties Black liquor chemical composition Black liquor behavior in the recovery unit (evaporators and

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] ).

in the industrial recovery unit (after Soderhjelm [3] ). Fig. 2. Simplified schematic representation of the

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. 3 a, 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. 3 b, 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. 3 b), 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. 3 a), 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 ( C ss < 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 ( C ss > 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

758 M. Cardoso et al. / Fuel 88 (2009) 756–763 Fig. 3. Schematic representation of lignin

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

Density ( q liquor )

(elementary analysis)

Organic/inorganic ratio (O/I) Calorific heating value (heating value, HV)

Lignin concentration ( C lig )

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

Lignin molar mass (MM lig )

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 C ss 6 17%), intermediate (38% 6 C ss 6 44%) and strong (63% 6 C ss 6 72%) li- quors have been taken and stored at 4 C. In the soda process mill, only samples of weak liquors (14% 6 C ss 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 re- quired 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 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) Nitrogen (N) Sodium (S)

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

[1,10]

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 BaSO 4 Liquor oxidation under pressure following potentiometric titration with AgNO 3

ABNT Test MB

 

106/65

 

Chlorine (Cl)

TAPPI Test T699

 

om-87

 

Silicon (Si) Lignin concentration ( C lig ) Molar mass (MM lig )

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

[2]

Lignin

[1,10,11]

[1,10]

Organic/inorganic

Organic to inorganic ratio (O/I)

[1]

materials

 

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 ( C lig ) and its molar mass (MM lig ) 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 MM lig (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 ( C ss ) is obtained by using the oven drying method at controlled temperature and the density ( q liquor ) 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 C ss 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 C ss 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 C ss [2,12,13]. Based on this s vs. D curves, the range of C ss , 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, C lig and MM lig , 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 ( C ss )

Liquor density at C ss

Dry a known mass of liquor in oven at controlled temperature until mass constant – Digital Metler balance AB204 (±10 4 g) Pycnometry (mass and volume measurements) – Digital Metler balance AB204 (±10 4 g), heater plate

TAPPI Test T650 om-89 [2]

Density

[2,12]

(

q liquor )

and standard 25 ml volumetric bottles

 

Calorific

Heating value (HV)

heating

Heating by a complete oxidizing liquor in an adiabatic calorimetric bomb (Shimadzu model C-03) TAPPI Test T684 om-90 [2]

value

Viscosity

Liquor apparent viscosity at C ss 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

[2,12]

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

HN

N aKS

 

C l

S i

Hardwood/ Eucalyptus grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Fibrous plant/ Bambasa vulgaris a Softwood/ Pinus sylvestris and Pinus caribaea b Hardwood b Hardwood/Eucalyptus b Fibrous plant/Straw c

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)

30.8

3.6

0.01

21.8

1.8

3.7

4.5

0.1

35.2

3.7

21.2

2.1

3.0

4.3

29.6

3.6

18.7

2.2

4.4

2.6

34.8

3.4

0.04

18.3

2.1

3.6

3.2

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

35.4

3.6

0.30

19.3

3.3

0.2

1.3

3.8

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

33.2

3.3

0.08

20.8

2.6

5.2

0.3

37.3

3.6

0.09

17.3

1.8

3.4

1.6

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 ( )

C lig (%) (mass per mass dry solids)

MM lig (Da)

Hardwood/ Eucalyptus grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Hardwood/ E. grandis a Fibrous plant/ Bambosa vulgaris a Softwood/ Pinus Caribaea b

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

1.81

42.3

820

17

2.2

40.2

1641

17

1.94

41.8

1401

17

2.1

42.3

1050

17

1.86 ± 0.09

39.7 ± 2.2

1871 ± 221

2.30

45.3

3282

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 Na 2 S 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 C lig 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 MM lig 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, MM lig 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, C lig and MM lig 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
Polystyrene standards
Lignin (Black liquor)
M.w 50000
M.w 382000
M.w 30000
M.w 17500
M.w 9000
M.w 2500
Toluen
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical
M.w 382000 M.w 30000 M.w 17500 M.w 9000 M.w 2500 Toluen 30 Time Fig. 4. Typical

30

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.

0

10

20

40

50

60

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, MM lig 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 MM lig 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 ( q liquor ) and viscosity ( g ). Results from earlier works [2,12] indicate that q liquor varies with C ss according to the following equation:

q liquor ¼

"

C ss

q

ss

þ ð1 C ss Þ

q

liq

#

1

ð

1Þ

where q ss is the density of the solid phase and q liq is the density of the liquid phase, both at the operating temperature. These densities, q ss and q liq , 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 q liquor with C ss 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.

Mill/liquor q ss (kg/m 3 ) q liq (kg/m 3 ) Mill A/eucalyptus 1926 (±258)
Mill/liquor
q ss (kg/m 3 )
q liq (kg/m 3 )
Mill A/eucalyptus
1926 (±258)
1005 (±20)
Mill C/eucalyptus
1936
1012
Mill F/bamboo
2098
947
1700
Mill A
Mill C
Mill F - bamboo
Equation 1- mill A
1500
Equation 1 - mill C
Equation 1 - mill F
1300
1100
900
0
20
40
60 80
ρ liquor (kg/m 3 )

C ss (%)

Fig. 5. Liquor density ( q liquor ) as a function of the solids concentration ( C ss ) 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/m 3 for eucalyptus liquor from mill A, ±5 kg/m 3 for eucalyptus liquor from mill C and ±42 kg/m 3 for bamboo liquor from mill F).

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 q liquor and C ss up to C ss = 0.65. For 0.65 < C ss < 0.80, changes in q liquor with C ss are more pronounced due to the liquor transition

from water-continuous phase to polymer-continuous phase. As shown in the q liquor vs. C ss curves of Fig. 5 , there is, for these liquors,

a transition region after which q liquor rises faster with an increase

in C ss . This occurs at C ss 0.50 for both eucalyptus liquor and at

C ss 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 C lig in the eucalyptus black liquor is 39.7 to 42.3%, little higher than C lig (39%) in the pine li- quor. This higher C lig 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, C lig in the bamboo liquor is 45.3% ( Table 5 ), higher than C lig in both, eucalyptus and pine, liquors. Zaman and Fricke [21] have reported that HV of slash pine li- quor varies strongly with C lig , but insignificantly with O/I. Their data are compared to HV data of the eucalyptus black liquor from

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

Mill/Liquor HV (kJ/kg) Mill A/eucalyptus 14593 (±162) Mill E/eucalyptus 14615 (±268) Mill F/bamboo 14673 (±226)
Mill/Liquor
HV (kJ/kg)
Mill A/eucalyptus
14593 (±162)
Mill E/eucalyptus
14615 (±268)
Mill F/bamboo
14673 (±226)
17000
eucalyptus liquor - mill E
pine liquor [21]
16000
15000
14000
13000
12000
11000
0.7
0.9
1.1
1.3
1.5
1.7
1.9
2.1
2.3
HV (kJ/kg)

O/I (-)

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] .

(cP)

η

(cP)

η

(cP)

η

762

M. Cardoso et al. / Fuel 88 (2009) 756–763

eucalyptus liquor - mill E 17000 pine liquor [21] 16000 15000 14000 13000 12000 11000
eucalyptus liquor - mill E
17000
pine liquor [21]
16000
15000
14000
13000
12000
11000
31
33
35
37
39
41
43
45
HV (kJ/kg)

C lig (%)

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

mill E, for varying O/I ( Fig. 6 ) and for varying C lig ( Fig. 7 ). Contrari- wise, the HV of the eucalyptus black liquor depends explicitly on O/I, but slightly on C lig . Both the organic components and the re- duced sulfur compounds in black liquor contribute to its heating values [4] . This non-expected result may indicate another organic compound presented at a significant concentration in the eucalyp- 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- ent 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 ( C ss ) and liquor temperature ( T ). The apparent black liquor viscosity is influenced 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 entan- gle more easily at low shear rates increasing the black liquor vis- cosity. At high shear rates, these macromolecules tend to align 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- er than one of the eucalyptus liquor, since the bamboo liquor has the highest value of MM lig ( 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. 8 b. These higher g values prevent an efficient evaporation of the bamboo li- quor 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 viscos- ity. 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. 8 a, one can see that, for C ss 6 40.5% at 30 C 6 T 6 40 C, the reological behavior of eucalyptus black li- quor approaches to a Newtonian fluid, with its viscosity indepen-

a 1050

900

750

600

450

300

150

0

b
50000

40000

30000

20000

10000

0

Css = 49.3% T= 35.3˚C Css = 51.5% T= 37.2˚C Css = 47,6% T= 37.3ºC
Css = 49.3% T= 35.3˚C
Css = 51.5% T= 37.2˚C
Css = 47,6% T= 37.3ºC
Css = 40.5% T= 31.5˚C
0 5
10
15
20
shear rate (s -1 ) Css = 35.9 % T = 29.5 ˚C Css =
shear rate (s -1 )
Css = 35.9 % T = 29.5 ˚C
Css = 37.8 % T = 29.5 ˚C
Css = 40.2 % T = 30.1 ˚C
Css = 37.8 % T = 69.5 ˚C
0 5
10
15
20

shear rate (s -1 )

Fig. 8. Liquor apparent viscosity, g , vs. shear rate, D , as function of C ss 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 C ss > 40.5%, its reological behavior is typical of a pseudoplastic fluid, with g decreasing expo- nentially 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 fluid for C ss 6 50%, corroborating the effect of lignin concentration and mass molar on

220

200

180

160

140

120

100

80

increasing D decreasing D 0 50 100 150 200 250
increasing D
decreasing D
0
50
100
150
200
250

shear rate (s -1 )

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

M. Cardoso et al. / Fuel 88 (2009) 756–763

763

the liquor viscosity. Although the bamboo liquor presents a similar behavior (see Fig. 8 b), its pseudoplastic behavior occurs at lower solid concentrations ( C ss < 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.

References

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