Influence the Ash Leaching of the Recovery Boiler

Electrostatic Precipitator on the Biological Treatment

effluent Kraft Pulp Mill Efficiency

Rafles A. da Mata: MSc student, UFV, Brazil, rafles.mata@ufv.br

Claudio Mudadu Silva: Full Professor, UFV, Brazil, mudado@ufv.br

Abstract

The ash leaching process of the electrostatic precipitator from the kraft pulp recovery boiler has been a
procedure adopted by modern pulp mills seeking the removal of chloride and potassium, minimizing fouling
and corrosion problems in the equipment and pipes of the recovery system. The ash leaching is an effluent
with high concentration of salts and high electrical conductivity. Such characteristics can affect the biological
treatment, especially in the biological sludge flocculation and microbial community, culminating in the solids
loss, low sludge quality, and consequently in efficiency reduction. This research aimed to evaluate the
influence of the ash leaching of the electrostatic precipitator of recovery boiler on the efficiency of the biological
effluent treatment of kraft pulp mill, when this stream is feed in a continuous and batch flow to the biological
reactor. The evaluation was carried out in three biological sequential batch reactors (R1, R2, R3) of 1000 ml
volume. Reactor R1 operated as a reference fed only with the wastewater from the pulp mill; Reactor R2 was
feed continuously with effluent pulp mill and ash leaching in fixed proportions that were increased gradually to
reach the real scenario. Reactor R3 was feed with the effluent pulp mill, and in batchwise with the ash leaching
effluent. All reactors maintained the same operating parameters, i.e, the dissolved oxygen OD>2 mg/L, COD:
N: P ratio equals to 250: 5: 1, hydraulic retention time equals to12 h. The study demonstrated that the presence
of ash leaching at certain concentrations affects negatively the biological treatment efficiency, worse the
bioflocculation and therefore causes solid losses in the sedimentation stage. And that the effect-chocking load
is more expressive.

Keywords: ash leaching; kraft pulp mill, biological wastewater treatment; activated sludge

Introduction
Modern kraft pulp mills have been adopting recovery boiler ash leaching procedures in order to maintain
acceptable levels of potassium and chloride concentrations in the black liquor. The liquid stream has been
normally sent to the effluent treatment plant.

Very little is known about the effects this stream can cause in the biological treatment plant. However, it has
been notice some mills a worsen sludge settleability and sludge losses since the employment of the recovery
boiler ash leaching units. It can be hypothesized that due to the ash leaching high salt concentration it may
have an effect over the biological wastewater treatment plant efficiency, , especially on the morphology of of
the floc, causing the sludge dispersion and therefore sludge losses in the secondary clarifier.

Ash Leaching has a high concentration of potassium and chloride, culminating in a very high electrical
conductivity of this stream that behaves as salt-affected substance which can inhibit the kinetics of the
microorganisms growth and flocculation Nitisoravut and Klomjek [3]., ,

Several studies have been published regarding effluent with high salinity and the behavior on biological
wastewater treatment systems. Wilén, et al [4], found that the addition of salts reduces the number of
filamentous bacteria, which are responsible for the macrostructure of the flocs, worsening the sludge
sedimentation in the secondary clarifier and increasing the loss of solids to the final effluent.

Studies have shown that inorganic salts may also affect the structure and properties of microbial flocs and
sedimentation, because of the decrease on the solubility and oxygen transfer to the liquid medium leading to

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
oxygen limitation. Therefore, high salt concentration in the effluent can cause negative effects on the biological
wastewater treatment plants, which affects the overall efficiency of the system [5].

The objective of the present work was to evaluate the influence of ash leaching on the efficiency of the
biological wastewater treatment of a kraft pulp mill.

Materials and methods

Effluent and Ash leaching

Effluent was obtained from a modern Brazilian eucalyptus bleached kraft pulp mill. The ash leaching was
obtained in laboratory by mixing ash from recovery boiler electrostatic precipitator and distilled water. The
proportion of water:ashes was 60:40 (weight basis). This proportion was chosen because of the final electrical
conductivity of the leaching around to 160 mS/cm, similar to industrial ash leaching.

Experimental Apparatus

The biological treatment system used consisted of three bench scale (1000 mL) sequential batch bioreactors,
(R1, R2, R3) equipped with air diffusion aerators and temperature controller as showed in Figure 1.

Figure 1. Experimental module.

Experimental methodology

Reactor 1 (R1) was used as a reference and was fed only with pulp mill effluent.

Reactor 2 (R2) was fed continuously with a mixture of pulp mill effluent and ash leaching. The proportion of
effluent:ash leaching that was fed to R2 was increased gradually every week. Initially the proportion was 1000:1
and was increased weekly to 1000:2, 100:3, until a final proportion of 1000:6. The proportion ratio of 1000:4 is
equivalent to the observed in most mills.

Reactor 3 (R3) was fed with pulp mill effluent and batchwise, every 24 hours, was applied a dosage of ash
leaching varied such as in the following proportions that were increased every week: 1000:4; 1000:8; 1000:12;

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
1000:16; 1000:20 and 1000:24 respectively. This reactor it was meant to evaluate the effect of chocking load
effect to the bioreactor.

The experimental procedures were performed in two phases. The first phase consisted of stabilizing the
reactors, in which all reactors were operated with a 12-hour cycle, with 11 h aeration and 1 h settling. This
phase was performed for a period of 15 days. All reactors which were fed only with the pulp mill effluent. The
bio-sludge used in the reactors was obtained from an activated sludge of a kraft pulp mill.

At every phase it was maintained a ratio of COD:N:P of 250:5:1 to maintain nutrients availability in the
bioreactors. Similarly, the dissolved oxygen was always maintained at a higher concentration of 2 mg/L. The
pH in the reactors was adjusted every cycle, and the temperature was kept at 35°C by means of an automatic
heating system coupled to a thermostat.

Analytical methodology

The analysis of pH, electrical conductivity, dissolved oxygen was carried out by using a multiparameter Hq40d
from Hach. Chemical Oxygen Demand-COD, Biochemical Oxygen Demand-BOD, Sludge Volumetric Index
(SVI) and Solids were performed according to procedures as described in the Standard Methods for the
Examination of Water & Wastewater [7].

The morphological sludge analysis was performed by a light microscope. Morphological assessment was
limited only to evaluate floc formation and filamentous bulking.

The analysis of the sludge biotic index (SBI) was based on microscopic identification and quantitation of the
fauna present in the reactors. The identification of organisms was carried out in pure sample disposed in simple
blade and viewed in optical microscope increased from 100 to 400-fold. In order to quantify the microorganisms
(protozoa and metazoan), the samples were diluted 10-fold with distilled water and placed on a crosslinked
Sedgwick-Rafter Camera with a 1 ml volume, and examined in a 100-fold increase lens [7].

Results and Discussion

In the first phase of the study, which consists in stabilizing the reactors has been found the following findings
(Figure 1).

The treatment system is stable in terms of COD removal from the 9th day of operation, where the COD is
reduced of 1217mg/L at an average of 360 mg/L, corresponding to a removal efficiency of greater than 70%.

The stabilization was carried in a little time, which means that the inoculum used was in good condition of
adaptability to the characteristics of fed effluent.

Figure 1. Stabilization of biological reactors, COD efficiency removal/ Solid concentration and sludge volumetric index.

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
In this phase, the concentrations of total suspended solid in the reactors were in the order of 940, 788 and 885
mg/L, respectively in reactors 1 to 3. The medium sludge volumetric index after stabilization show values of
135, 134 and 122 mg/L respectively in the three reactors, which means an average sedimentation, according
to Von Sperling [9].

Like all reactors only feed wiht the pulp mill effluent, the electrical conductivity in all the reactors was around
4,5mS/cm, characterizing a normal condition of operation.

In Sequency after the stabilization phase was initiated the verification of the influency of ash leaching on the
biological treatment.

The treatment whit the insertion of ash leaching had a duration of six week, every week was varied the dosage
of ash leaching on ratio the effluent volume input on the system, as on methodological procedure. The
conductivity variations on the system caused due to ash leaching achieved considerable values, as showed in
figure 3.

10,00
9,00
8,00
7,00
mS/Cm

6,00
5,00
4,00
3,00
2,00
1,00
0,00
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85
Days
Reactor 1 Reactor 2 Reactor 3

Figure 3. Variation of electrical conductivity.

The figure 3 above, show the profile of conductivity in all phase of the system. In the period until 22-days
(stabilization phase), the electrical conductivity was maintained around 5 mS/cm. After stabilization phase,
note the dosage of ash leaching caused an effect substantial on the profile the conductivity, increasing the
value of electrical conductivity level on the reactors 2 and 3.

High electrical conductivity in the medium indicat high salt concentrations. According to Dalmacija et al [6] can
impair the biological treatment, whereas the high salt concentration on the medium impedes the transport of
chemical species between the environment and the interior of the microbial cell. And can also cause changes
in the metabolism and inhibiting effects as well as due to the large difference in osmotic pressure between the
cytoplasm and the environment, there is a tendency to cause dehydration and cell lysis in microorganisms.

So was evaluted the COD removal in the system on every dose increment of ash leaching, the results obtained
are showed in Figure 4.

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
 1400 10,0
1200 9,0
8,0

C.E (mS/cm)
COD (mg/L)

1000 7,0
800 6,0
5,0
600 4,0
400 3,0
200 2,0
1,0
0 0,0
1 2 3 4 5 6
Dosage of ash leaching
COD input Reactor 1 Reactor 2
Reactor 3 Reactor 1- C.E Reactor 2- C.E
Figure 4. Evolution of COD / variations of conductivity by according to the dosage of ash leaching (Dosage of ash leaching
in the reactor 2: 1- 1000:1, 2- 1000:2, 3- 1000:3, 4- 1000:4, 5- 1000:5, 6-1000:6. Dosage of ash leaching in the reactor 3:
1- 1000:4, 2- 1000:8, 3- 1000:12, 4- 1000:16, 5- 1000:20 e 6- 1000:24).

The CDO in output in bioreactor 1(reference) was maintained below to 400mg/l, the electrical conductivity
remains constant. While that the output of bioreactor 2 reaches value above of 400mg/L after the third dosage,
in this moment the electrical conductivity is 7mS/cm approximate. Similar like in the bioreactor 3, however,
higher values of COD and the electrical conductivity that reaches 10mS/cm.

with the increase dosage of ash leaching occurs higher value electrical conductivity, that result in loss COD
efficiency removal, describing a scenario commonly discussed in literature[4] [6] that one of salinity effects is
the difficult treatability, due to alterations of net mass that difficult or inhibit the metabolic actions of
microorganisms. Note that the result for to bioreactor 3, in chocking load, was more expressive.

The evaluation of solid loss in treated effluent through of settleable solid showed in figure 5.

Figure 5. Solid loss in treated effluent – bioreactor 1 reference – bioreactor 2, feed ash leaching continuously.

It’s observed that in reactor 1, the volume of solid loss is constant around 30ml/L. Reactor 2 during the fourth
dosage, the solid loss is expressive (around 50ml/L), after there are decrease solid loss for values around
20ml/L.

The values below to 20ml/L the settleable solid on the treated effluent in reactor 2, is less as on the reactor 1.
That may explain by decrease solid concentration on the reactor 2. How showed in figure 6.

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
 1000 10,0
900 9,0
800 8,0

C.E (mS/cm)
TSS (mg/L)

700 7,0
600 6,0
500 5,0
400 4,0
300 3,0
200 2,0
100 1,0
0 0,0
1 2 3 4 5 6
Dosage of Ash Leaching

TSS- Reactor 1 TSS- Reactor 2 TSS- Reactor 3

C.E - Reactor 1 C.E- Reactor 2 C.E -Reactor 3

Figure 6.Total Solids Suspended / variation of the electrical condutivity acording to dosage of ash leaching.

The solid concentration in constant in reactor 1 (900mlg/L). In reactor 2 is reduced from 900 – 700mg/l
approximated. Reactor 3 reduced from 900- 600mg/L.

It was observed the solid concentration in the reactors 2 and 3 is significantly reduced every ash leaching
dosage. According to increasing electrical conductivity in reactors, decrease the solid concentration, because
there is a solid loss on the system.

The solid loss possibly correlates with reduction in the COD efficiency removal because the reduction biomass
unbalance ratio Feed/Microorganisms (F: M) affecting the time answer of treatment system.

The solid loss may be observed also monitoring solid settleable in the reactors (Figure 6).

Figure 6. Solid settleable in the reactors

On the beginning the solid volume of 70-80ml/L for the all reactors. Every dosage of ash leaching the solid
volume in the reactors (2 and 3) were constantly reduced. After the third dose when the proportion (effluent:
ash leaching) were higher than 1000:3 for the reactor 2 and greater than 1000:12 to the reactor 3, noted that
there are a sudden solid volumes reduction. Thus, it is understood that in terms of solids loss to the system
becomes sensitive to the above of the dosages mentioned.

The effect of ash leaching like chocking load it still more expressive (figure 7).

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
Figure 7. Solid loss in treated effluent – bioreactor 1 reference – bioreactor 2, feed ash leaching continuously.

Note the solid loss significantly higher on the reactor 3. In effect choking load every 24 hours. From the first
dosage, solid loss in reactor 2 was bigger than reactor 1 (reference). Only after fifth dosage, the solid loss was
decrease for to values below of the reactor 1 coinciding whit the little solid concentration in the reactor. This
fact indicates that intermittent loads of saline effluents or with high electrical conductivity results in more severe
disorders to a biological treatment system.

Another factor evaluated throughout the treatment period and for variations in dosages Ash Leaching was the
morphology of microbial flocs and sludge biotic index.

Notes that regarding the structure of microbial floc, at any stage of the treatment was not observed flocs with
a large variation in size of the aggregates, generally are all presented with uniformity, and do not have large
amounts of filaments out on the aggregates, the that indicates the proper balance between the microorganisms
flocculent and filamentous (Figure 8).

According to Jenkins et al [7], good training flake is given by consortium among microorganisms, and it is
extremely important for the operation of the treatment system, so it is possible to evaluate the condition of a
station by means of microscopy analysis, which demonstrate with ease if there is any disturbance in the
system. Accordingly, regarding the morphology of the flocs, the doses administered of ash leaching did not
cause changes in the system as perceived.

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
 Figure 8. Characterization of biological flocs. view 10x /0.22.

As regards the sludge biotic index or microbiological characterization, the microscope examination showed
that the sludge generally in all treatments showed a diverse Microfauna composed by protozoa (natant free
background of furniture and sessile) and amoeboid (Tacamebas, Aracella) and micrometazoários
representatives of rotifers and nematodes (Table 1).

In general, throughout the evaluation period was observed the predominance of Aspidisca sp, Aracella sp, and
rotifers. Other common groups observed were flagellated, the Chilodonella sp, Euglyphia sp, Acanthamoeba.
And in the groups little observed are the Nematodes, Vorticella, Epistylis and Holophrya.

Therefore, it should be noted that the Vorticella group, Epistylis and nematodes have become more frequently
observed in the reactor with presence of ash leaching, and more expressive in the final stages treatments that
were the highest concentrations. according Madoni [8], the excessive presence of this group of
microorganisms may indicate low efficiency of the treatment system.

The predominant appearance of Aspidisca sp indicates an excess of oxygen dissolved in the middle. The
predominance of Aracella of the genus tacamebas, the presence of rotifers, nematodes, are indicators that the
system is stable operating conditions, low organic load and high oxygen concentrations, high sludge age, good
nitrification efficiency and good quality of the effluent end [8].

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
Table 1 - Composition and frequency of the microbiota of the biological reactors

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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.
Conclusions
The ash leaching having electrical conductivity value of the order of 170mS/cm, can significantly change the
characteristic of electrical conductivity of the treatment plant, increasing the level 4 for the range of 7ms / cm
approximated.

The biological treatment system supports loads of ash leaching until the dosage of 1000:3 in continuously
feed. Proportion above 1000:3 cause reduction on the efficiency COD removal.

Chocking-loads still the proportion 1000:4 (first dosage) is sufficient to cause reduction of efficiency organic
matter removal, and increase the solid loss.

The sludge biotic index did not change significantly, of the form noticeable of according to the data evaluted.

References

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Conselho Nacional do Meio Ambiente-CONAMA. Publicado no D.O.U.

3. WILÉN, B.M. et al. Relationship between floc composition and flocculation and settling properties
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6. APHA (1998). Standard Methods for the examination of water and wastewater. American Public Health
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7. Jenkins, D., Richard, M.G., Daigger, G.T., 1993. Manual on the Causes and Control of Activated
Sludge Bulking and Foaming, 2nd ed. Lewis Publishers, Chelsea, MI.

8. Madoni, P., 1994. A sludge biotic index (SBI) for the evaluation of the biological performance of
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7th International Colloquium on Eucalyptus Pulp, May 26-29, 2015. Vitória, Espirito Santo, Brazil.