Journal of Environmental Management 113 (2012) 399e406

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Journal of Environmental Management

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Treatment of wastewater from pulp and paper mill industry by electrochemical

methods in membrane reactor
Kanjana Chanworrawoot a, Mali Hunsom b, c, *
a
Department of Environmental Science, Faculty of Science, Chulalongkorn University, 254 Phayathai Rd., Bangkok 10330, Thailand
b
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, 254 Phayathai Rd., Bangkok 10330, Thailand
c
Center of Excellence on Petrochemical and Materials Technology (PETRO-MAT), Chulalongkorn University, Bangkok 10330, Thailand

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

Article history: The treatment of wastewater from a pulp and paper mill plant using electrochemical methods was
Received 15 May 2012 performed at a laboratory bench-scale at ambient temperature (w30
C). The effects of wastewater
Received in revised form dilution (10- to 100-fold), circulating water flow rate (0e3.95 l/min), current density (1.90e3.80 mA/cm2)
30 August 2012
and sodium chloride concentration (0e3.75 g/l) were ascertained. The results demonstrated that this
Accepted 18 September 2012
Available online 11 October 2012
methods can facilitate the disappearance of the oxidative coupling unit of lignin as well as other organic
and inorganic compounds, measured in terms of the removal of color, total biological- and total chemical
oxygen demand (BOD and COD), and the total suspended and dissolved solids (TSS and TSD). In addition,
Keywords:
Pulp wastewater
the electrochemical method was more effective at reducing the pollutant levels, produced a smaller
Anionic membrane quantity of low-density sludge and had a low operating cost per unit quantity of COD. After optimization,
Treatment the electrochemical method operating in a batch mode enhanced the removal of color, BOD and COD at
Electrochemistry around 98%, 98% and 97%, respectively, whilst in a continuous mode at the steady state condition (8 h
after the start-up time) the color, BOD and COD levels were reduced by around 91%, 83% and 86%,
respectively.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction ultrafiltration) (Ksibi et al., 2003). Although activated sludge plants

The pulp and paper mill industries consume a large amount of
fresh water and discharge a large quantity of effluents with a high
organic and inorganic pollution loading. Among the various pulp-
ing stages (wood preparation, pulping, pulp washing, screening,
washing, bleaching, and paper machine and coating operations),
the chemical pulping stage generates high pollutant strength
wastewater that contains wood debris and soluble wood materials
(Pokhrel and Viraraghavan, 2004). Several previous works have
reported that the discharging of untreated pulp and paper mill
wastewater impacted all aspects of the environment, including the
water, air and land (Erisction and Larsson, 2000; Archibald, 2000;
Makris and Banerjee, 2002).
Practically, the main treatment processes used at pulp and paper
mill plants are the primary clarification (sedimentation or flota-
tion), secondary treatment (activated sludge process or anaerobic
digestion) and/or tertiary processes (membrane processes, such as
* Corresponding author. Department of Chemical Technology, Faculty of Science,
Chulalongkorn University, 254 Phayathai Rd., Bangkok 10330, Thailand. Tel.: þ66 2
2187523; fax: þ66 2 2555831.
E-mail address: mali.h@chula.ac.th (M. Hunsom).
have been the most common wastewater treatment process used
for the removal of the organic product components in several
countries including Thailand, there are several problems with the
process. It produces sludge with very variable settlement proper-
ties, it is sensitive to shock loading and toxicity, and its capacity to
remove poorly biodegradable toxic substances is limited. Therefore,
many researchers have attempted to develop new technologies for
complementing or even replacing some of these treatments, such
as physicochemical treatment (Amat et al., 2005; Ko et al., 2009; Li
and Zhang, 2011; Wang et al., 2011) or biological treatment and
algal (Tarlan et al., 2002; Buzzini et al., 2005; Juan et al., 2005; Cui
et al., 2011).
Besides, the electrochemical treatment process has recently
attracted considerable attention due to its variety of applications
for various kinds of industrial wastewater that contain both organic
and inorganic substances. For pulp and paper mill wastewater, the
electrochemical treatment can enhance the maximum improve-
ment of the biodegradability index of the Decker filtrate stream
from 0.11 to 0.46 at the optimum operating conditions with an
acceptable current efficiency and specific energy consumption in
terms of economic feasibility (Soloman et al., 2009). The presence
of the kaolin catalyst in the combined electro-catalysis in

0301-4797/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jenvman.2012.09.021
400 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406

conjunction with the Cu2 OeCoOePO3 4 modified kaolin can facili-

tate a higher COD removal level due to the large quantity of oxidant
(OH) that is produced from the synergetic effect between the
modified kaolin and the electrochemical system (Wang et al.,
2007). Within the electrocoagulation process the presence of
polyelectrolytes, such as sodium silicate, calcium carbonate and
polyacrylamide, had no significant effect on the treatment process
(Khansorthong and Hunsom, 2009). However, it can be omitted
saving on operational and environmental costs.
In this work, the actual wastewater obtained from a pulp and
paper mill plant was treated by the electrochemical methods. Based
on our treatment approach, instead to add large amount of mineral
acid such as H2SO4, the in-situ Hþ can be produced in the system by
electrochemical technique, resulting to a small production of low-
density sludge, low operating cost as well as low cost for down-
stream treatment due to small contamination of chemical in
treated wastewater. The benefit of this method was determined in
terms of the removal efficiency and the operating cost was
investigated.

2. Experimental

The wastewater used in this work was collected from the diges-
tion house unit of a pulp and paper mill industry. The treatment of
the actual wastewater from the pulp and paper mill industry was
performed at a laboratory bench-scale at ambient temperature
(w30
C) by electrochemical methods in a membrane electro-
chemical reactor in either a batch or a hybrid batch-continuous mode
(Fig. 1). The electrochemical cell, made from Plexiglas with
a dimension of 0.10  0.10  0.11 m, was separated into the anodic
and cathodic compartments by an anionic membrane (IONAC type
MA-3475). Commercial Ti/RuO2 grids (total surface area of
0.0011 m2) and stainless steel (total surface area of 0.0141 m2) was
used as the anode and cathode, respectively. For each experiment,
0.8 l of acidic distilled water and 0.8 l of pulp and paper mill waste-
water were filled in the anodic and cathodic compartments, Fig. 1. Experimental set up for the (A) batch and (B) hybrid batch-continuous opera-
respectively. To promote a good mass transfer in the system, tion modes of the electrochemical cell. (1) D.C. power supply, (2) anode, (3) anionic
a magnetic pump (SANSO, PMD-0311) was used to circulate the membrane, (4) cathode, (5) reactor, (6) pump, (7) valve, (8) inlet stream, (9) outlet
stream, (10) wastewater storage tank, (11) peristaltic pump, and (12) receiver tank for
electrolyte in the reactor. A regulated DC power supply (GPS-
treated wastewater.
3030DD) was employing to supply the external DC electricity. For the
hybrid batch-continuous mode operation (which over longer run
times would simplify to a continuous operation mode), the experi- higher than the acceptable (Thai) standard values by approxi-
mental set up was the same as that above for the batch operation mately 1500- to 1800-fold, 324- to 344-fold, 56- to 60-fold and 6.65- to
mode except that additional fresh wastewater was supplied from the 6.8-fold, for BOD, COD, TDS and TSS, respectively.
storage tank into the reactor by a peristaltic pump (Masterflex, Model As demonstrated in the FTIR spectra (Fig. 2(a)), the original
77200-60) and the treated wastewater overflowed from the top of wastewater from the pulp and paper mill contained most of the
reactor to the receiver tank. The set up was run as a batch mode (i.e. characteristic absorption bands of organic contaminants (Sun et al.,
inflow rate of zero) for the first 3 h, and then as a continuous mode 1999; Jin et al., 2005; Xueyan et al., 2008), assigned as follows. A
thereafter at the indicated wastewater inflow rate. During the huge shoulder at the wavelength of 3200e3600 cm1 is assigned to
treatment, the properties of the wastewater, including the total BOD, the OeH stretching of hydroxyl groups. A small band at 1698 cm1
total COD, TDS and TSS were analyzed at time intervals following the can be assigned to be conjugated carbonyl groups. Absorptions at
standard method (APHA, 1998), whilst the color intensity was char- 1640 and 1530 cm1 indicate the typical aromatic skeletal vibra-
acterized using UVevisible spectrophotometry (Jasco, V-530). The tion. The intense bands at 1366 cm1 are associated with syringyl
significant difference of each parameters between treatments was ring breathing with CO stretching, the small bands at 1275 cm1
tested by one-way ANOVA at the level of confidence of 95% (p ¼ 0.05). correspond to the guaiacyl ring breathing with CeO stretching
while the small peak at 1039 cm1 is assigned to aromatic CeH
3. Results and discussion guaiacyl type and C H deformation of primary alcohol. The pres-
ence of syringyl- and guaiacyl units, the oxidative coupling unit of
3.1. Properties of wastewater lignin, indicates the presence of lignin in the wastewater.

The original wastewater was a non-viscous black liquid with a basic
pH (range 12.8e12.94), and had a high concentration of pollutants,
well above the limits of the Thai government standard for discharge
to the environment (Table 1). Specifically, the concentrations of BOD,
COD, total dissolved solids (TDS) and total suspended solids (TSS) were
3.2. Pollutant removal by the electrochemical technique in a batch
mode
As mentioned previously (Wadekar et al., 2009), the acid
precipitation method is expensive due to requirement for large
 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406 401

Table 1
Chemical and physical properties of the pulp and paper mill wastewater before treatment (Raw) and after electrochemical treatment.

Properties Thai standard Raw wastewater Properties of wastewater after treatment

Electrochemical method (batch)a Electrochemical method (continuous)b

pH 5.5e9.0 12.8e12.94 1.92 1.94
COD (mg/l)  400 129,600e137,600 92 352
BOD (mg/l)  60 90,000e112,000 60 300
Color (Pt-Co unit) Not objectionable 1,030,650e1,505,000 678 2393
TDS (mg/l) 3000 154,833e178,540 9475 9945
TSS (mg/l) 150 683e1020 85 130
Temperature (
C) 40 25e29 44.5 39
Conductivity (mS/cm) 193.3e199.5 NAc NAc
a,b
Treatment in a membrane electrochemical reactor in abatch or chybrid batch-continuous operation mode at a current density of 2.53 mA/cm2, circulating flow rate of 3.46 l/
min, initial wastewater pH and dilution of 11.87 and 50-fold and NaCl at 2.0 g/l for a3 h or b8 h electrolysis time. For the bcontinuous operation mode the wastewater feed rate
was 4 ml/min cNA ¼ not analyzed.

amounts of sulfuric acid and the logistic and environmental prob- oxidation products (Nagarathnamma et al., 1999), as summarized
lems of large scale operation with a corrosive and non-ecofriendly generically in reactions (3) and (4).
acid including the disposal of large volumes of highly acidic water.
As an alternative, the in-situ Hþ production was carried out using an
electrochemical membrane reactor with a Ti/RuO2 electrode. At the R þ MOx ðOHÞz 4CO2 þ zHþ þ ze þ MOx (3)
cathode, the reduction of H2O to OH and gaseous H2 occurs,
whereas, at the anode the oxidation of H2O to Hþ and gaseous O2
R þ MOxþ1 4RO þ MOx (4)
occurs (summarized in reactions (1) and (2)).

2H2 O þ 2e /2OH þ H2 (1) 3.2.1. Effect of dilution

2H2 O/4Hþ þ O2 þ e
The generated Hþ can react with the lignin, tannin and inorganic
compounds in the wastewater as per the acid (chemical) treatment
method, resulting in the precipitation of such compounds from the
wastewater and so leading to lower amount of color, BOD and COD
in the system. However, in addition to this the precipitation of
pollutants by the generation of Hþ in the membrane electro-
chemical reactor, the pollutants might also be removed by the
reaction with the oxidizing OH radical generated by the physically
adsorbed active oxygen (adsorbed hydroxyl radicals, MOx(OH)z) or
the chemisorbed active oxygen (oxygen in the oxide lattice, MOxþ1)
on the electrode surface. This physically adsorbed active oxygen can
cause the complete combustion of organic compounds (R), and the
adsorbed active oxygen can participate in the formation of selective
Because the untreated pulp and paper mill wastewater con-
tained a high concentration of pollutants with a high fluctuate
(2)
value (Table 1), the effect of dilution of the wastewater, in terms of
the total volume of wastewater divided by the sample volume, was
performed using a dilution of 10-, 50- and 100-fold maintaining the
current density at 1.90 mA/cm2, an initial wastewater pH of 12.94
without mixing (circulating flow rate of zero). The raw wastewater
contained color, BOD, COD, TDS and TSS levels of approximately
1,278,000 Pt-Co unit, 112,000 mg/l, 133,867 mg/l, 154,833 mg/l and
683 mg/l, respectively. Within the dilution range studied,
increasing the dilution of the wastewater resulted to a significant
reduction of BOD level with F (p ¼ 0.05) of 639 (Table 3). For COD
(Fig. 3(c)) and color (Fig. 3(a)) were significantly increased with
increasing dilutions of the wastewater with F (p ¼ 0.05) of 4683 and
80,894, respectively (Table 3). For example, the significant decrease
of color and COD was observed after 3 h electrolysis from 4267 Pt-

Fig. 2. FTIR spectra of the (a) untreated wastewater from pulp and paper mill industry and (b,c) after treatment by the optimized electrochemical technique operating in a (b) batch
and (c) hybrid batch-continuous operation mode.
402 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406

Table 2 fresh water used, a 50-fold wastewater dilution was selected as

Operating cost analysis of lignin-contaminated wastewater treatment by electro- optimal for further trials.
chemical method.

Types of process Raw data per m3 Total cost 3.2.2. Effect of circulating flow rate
wastewater The effect of varying the circulating flow rate (mixing) of the
USDa/m3 USD/kg COD
I. Electrochemical method (batch)b wastewater in the electroprecipitation reactor was then investi-
Electricity (kWh) 67.5 21.03 10.15 gated within the range of 0e3.46 l/min, maintaining a current
Additive (kg) 2.5 density of 1.9 mA/cm2 with an initial wastewater pH and dilution of
Sludge (kg) 0.15
11.87 and 50-fold. Increasing the circulating flow rate of the
II. Electrochemical method (continuous)c wastewater led to a higher pollutant removal, particularly for the
Electricity (kWh) 79.2 21.00 12.48 color and COD removal (Fig. 4 and Table 3). For example, a circu-
Additive (kg) 0.48
lating flow rate of 2.64 l/min enhanced the removal efficiencies of
Sludge (kg) 0.0078
color and COD after 3 h electrolysis time by about 8% and 9%,
b,c
Treatment in a membrane electrochemical reactor in cbatch or dhybrid batch- respectively, above that obtained with no water circulation in the
continuous operation mode at a current density of 2.53 mA/cm2, circulating flow
rate of 3.46 l/min, initial wastewater pH and dilution of 11.87 and 50-fold and NaCl
reactor. This might be due to the improved contact between the
at 2.0 g/l for c3 h or d8 h electrolysis time. For the ccontinuous operation mode the active species (Hþ/OH) and the pollutant in the presence of
wastewater feed rate was 4 ml/min. circulating water. Nevertheless, flow rates of more than 2.64 l/min
a
1 USD ¼ 30.95 Baht. did not promote any further higher color, BOD or COD removal,
indicating the limitation of the kinetics of pollutant precipitation
Co unit to 256 Pt-Co unit and from 8756 mg/l to 699 mg/l, during this period. With regard to the change in the TDS and TSS
respectively, as the wastewater dilution level was increased from levels in the treated wastewater, they decreased as the circulating
10-fold to 100-fold. This is because, at a low wastewater dilution flow rate increased (data not shown). This may be due to the fact
(high concentration of pollutants) the electrically generated Hþ that a high circulating flow rate provided a high chance of collision
concentration or the Hþ: pollutant molar ratio in the system may between each precipitate species. Taking this into account as well,
not be adequate to precipitate the contained pollutants. In contrast, a circulating flow rate of 3.46 l/min was selected as optimal for
the TDS and TSS levels both increased with both increasing elec- further work.
trolysis time and with increasing wastewater dilutions (data not
shown), presumably due to the formation of small suspended 3.2.3. Effect of the current density
species during the treatment process. Considering in addition the The effect of varying the current density on the removal effi-
TDS and TSS levels, plus the volume of wastewater produced and ciency of all pollutants was evaluated over the range of 1.9e

Table 3
One-way ANOVA table.

Parameters Source of variance Sum of squares Degrees of freedom Mean square F (p ¼ 0.05) Fcrit Meaning
Dilution COD Between treatments 118,230,365 2 59,115,182 4638 5.1 Significant
Residual 76,476 6 12,746
Total 118,306,841 8
BOD Between treatments 115,257 2 57,628 639 5.1 Significant
Residual 541 6 90
Total 115,798 8
Color Between treatments 29,478,736 2 14,739,368 80,894 5.1 Significant
Residual 1093 6 182
Total 29,479,829 8 0
Flow rate COD Between treatments 233.1 3.0 77.7 398.4 4.1 Significant
Residual 1.6 8.0 0.2
Total 234.7 11.0 0.0
BOD Between treatments 12.4 3.0 4.1 1.5 4.1 Not Significant
Residual 22.1 8.0 2.8
Total 34.5 11.0 0.0
Color Between treatments 233.0 3.0 77.7 547.3 4.1 Significant
Residual 1.1 8.0 0.1
Total 234.1 11.0 0.0
Current density COD Between treatments 260.4 3.0 86.8 231.0 4.1 Significant
Residual 3.0 8.0 0.4
Total 263.4 11.0
BOD Between treatments 161.3 3.0 53.8 44.2 4.1 Significant
Residual 9.7 8.0 1.2
Total 171.1 11.0
Color Between treatments 713.7 3.0 237.9 4872.0 4.1 Significant
Residual 0.4 8.0 0.0
Total 714.1 11.0
NaCl concentration COD Between treatments 1082.5 4.0 270.6 1059.8 3.5 Significant
Residual 2.6 10.0 0.3
Total 1085.1 14.0
BOD Between treatments 32.7 4.0 8.2 Not Significant
Residual 66.5 10.0 6.6 1.2 3.5
Total 99.2 14.0 0.0
Color Between treatments 44.3 4.0 11.1 Significant
Residual 3.0 10.0 0.3 36.6 3.5
Total 47.3 14.0 0.0
 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406
Fig. 3. Evaluation of the (a) color, (b) BOD and (c) COD removal levels as a function of
the electrolysis time in an electrochemical cell operating in batch mode with
a wastewater dilution level of 10-fold (>), 50-fold (,) and 100-fold (6).
3.80 mA/cm2, maintaining the circulating flow rate of 3.46 l/min
and the initial wastewater pH and dilution of 11.87 and 50-fold. As
expected, the current density affected significantly on the removal
efficiencies of all investigated pollutants (Fig. 6 and Table 3).
Increasing the current density from 1.90 to 3.80 mA/cm2 increased
the color, BOD and COD removal within the first hour of electrolysis
time from 83%, 75% and 35% to 90%, 90% and 70%, respectively. This
is because a large amount of the active reactant species (Hþ/OH)
would be produced at a high current density according to Faraday’s
law, leading to lower amount of pollutants in the wastewater.
However, too high an applied current density, such as at 3.80 mA/
cm2, led to a decrease in the removal efficiency of color and COD at
longer (from 1.5 to 2 h onwards) electrolysis times (Fig. 5(a) and
(c)). This is because at the higher applied current densities a high
system temperature is generated (>50
C in this case), leading to
the re-dissolution of precipitated molecules into the treated
wastewater (Viboon et al., 2006). The TDS levels increased as both
the current density and the electrolysis time increased (data not
shown), presumably due to the fact that a high current density in
the presence of a long electrolysis time causes a high level of
destruction and precipitation of organic and inorganic compounds,
resulting in the increase in the TDS in the system (Ram et al., 1999).
403
Fig. 4. Evaluation of the (a) color, (b) BOD and (c) COD removal levels as a function of
the electrolysis time in an electrochemical cell operating in batch mode with a flow
rate of 0.00 l/min (), 2.64 l/min (>), 3.46 l/min (,) and 3.95 l/min (6).
On the other hand, the TSS levels increased significantly to 749 and
595 mg/l within 1 h at a current density of 1.90 and 2.5 mA/cm2,
respectively, and then dropped to 560 and 110 mg/l, respectively, at
5 h electrolysis time (data not shown). This might be due to the
coagulation of suspended solids in the wastewater and their
settling out during the long electrolysis times.
The optimum current density was determined by using the
instantaneous current efficiency (CE) calculated at each specified
time according to Eq. (5) (Rajkumar et al., 2005).
ðCODÞt  ðCODÞtþDt
CEð%Þ ¼ FL100 (5)
8I Dt
From the plot in Fig. 6, the CE increased sharply from zero to
approximately 15% during the first 15 min and then dropped
rapidly to around 2e5% from 1 h of electrolysis time onwards. This
decrease in the CE may be attributed to the adsorption of organic
species, such as lignin, tannin, polysaccharide or other inorganic
compounds, on the electrode surface. From the results of this part,
the optimum current density was selected at 2.53 mA/cm2.
404 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406

100 circulating flow rate of 3.46 l/min and the initial wastewater pH and
dilution of 11.87 and 50-fold. As demonstrated in Table 3, the
additive concentration influenced significantly on the removal
Color removal (%)

80
percentages of COD and color, but not BOD at 95% confidential
60 (Fig. 7 and Table 3). For example, increasing the NaCl concentration
from 0 to 2.5 g/l led to an increase in the removal efficiencies of
40 color and COD from 91% to 97% and from 77% to 97% within 3 h
electrolysis time, respectively. This might be attributed to the
20 destruction of organic compounds by the active chloro species (Cl2/
a OCl) generated in the presence of Cl ions (Rajkumar et al., 2005;
0 Zhang et al., 2006). In the presence of NaCl, the active chloro species
0 1 2 3 4 5 would be first generated in the system as summarized in reactions
Time (h)
(6)e(8).
100
2Cl /Cl2 þ 2e (6)
80
BOD removal (%)

Cl2 þ H2 O/HOCl þ Hþ þ Cl (7)

60

40 HOCl/Hþ þ OCl (8)

20 The chloric acid (OCl), collectively referred to as “active chlo-

b rine”, can react with the various pollutants (R) leading to the
0
100
0 1 2 3 4 5
Time (h)
80
Color removal (%)

100
60
80
COD removal (%)

40
60
20
40 a
0
20 0 1 2 3 4 5
c Time (h)
0 100
0 1 2 3 4 5
Time (h) 80
BOD removal (%)

Fig. 5. Evaluation of the (a) color, (b) BOD and (c) COD removal levels as a function of the
60
electrolysis time in an electrochemical cell operating in batch mode with current
densities of 1.90 mA/cm2 (>), 2.53 mA/cm2 (,), 3.16 mA/cm2 (6) and 3.80 mA/cm2 ().
40
3.2.4. Effect of the additive (NaCl) concentration
To achieve a higher removal efficiency of all the pollutants in the 20
pulp and paper mill wastewater, NaCl was added in the range of 0e b
3.75 g/l, maintaining the current density at 2.53 mA/cm2, 0
0 1 2 3 4 5
Time (h)
20
100

15 80
COD removal (%)
CE (%)

60
10

40
5
20
c
0 0
0 1 2 3 4 5 0 1 2 3 4 5
Time (h) Time (h)

Fig. 6. Evaluation of the current efficiency (CE) as a function of the electrolysis time in Fig. 7. Evaluation of the (a) color, (b) BOD and (c) COD removal levels as a function of
an electrochemical cell operating in batch mode with current densities of 1.90 mA/cm2 the electrolysis time in an electrochemical cell operating in the batch mode in the
(>), 2.53 mA/cm2 (,), 3.16 mA/cm2 (6). presence of NaCl at 0.00 g/l (þ), 0.63 g/l (>), 1.25 g/l (,), 2.50 g/l (6) and 3.75 g/l ().
 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406 405

formation of intermediate species (reaction (9)), where if complete 100

oxidation occurs the final products are CO2 and H2O (reaction (10)).
80

Color removal (%)


OCl
R / Intermediate species þ CO2 þ H2 O (9)
Fast 60
S1 S2
OCl
 40
Intermediate species / CO2 þ H2 O (10)
Slow
20
a
The presence of NaCl at all tested concentrations enhanced the 0
reduction of TDS and TSS levels in comparison with that in the 0 1 2 3 4 5 6 7 8 9 10
absence of NaCl (data not shown). This is because the generated Time (h)
active chlorine can promote a greater level of complete oxidization 100
of pollutants in the wastewater to CO2 and H2O, and so lower the
TDS and TSS quantity in the system (Chen, 2004). However, the use 80

BOD removal (%)

of Cl-containing electrolytes is highly questionable to the inevitable
formation of very toxic organo-chlorinated by-products. Thus, the 60
operator should analysis as well the properties of treated
S1 S2
wastewater. 40
The properties of the treated wastewater by the electrochemical
20
technique operating in a batch mode at the above derived optimum
b
conditions are shown in Table 1. The BOD, COD and TSS levels were
within the acceptable range of the Thai government standard for 0
environmental discharge, whilst the color of treated wastewater is 0 1 2 3 4 5 6 7 8 9 10
relatively clear and not objectionable. This is because the electro- Time (h)
chemical technique can facilitate the reduction/elimination of 100
organic or inorganic compounds, particularly lignin, is supported
COD removal (%)
by the disappearance of the oxidative coupling unit of lignin 80
(syringyl unit at 1275 cm1 and guaiacyl unit 1039 cm1) in the
FTIR spectra (Fig. 2(b)). However, the TDS level of the electro- 60
chemical treated wastewater was still 3.16-fold greater than the
40 S1 S2
acceptable Thai standard value, indicating that the electrochemical
technique is not effective in reducing the TDS levels in wastewater
20
sufficiently. Although the pH of the treated wastewater was too
c
acidic, it could be neutralized by the basic solution obtained in the 0
cathodic compartment.
0 1 2 3 4 5 6 7 8 9 10
Time (h)
3.3. Pollutant removal by electrochemical technique in hybrid
batch-continuous mode Fig. 8. Evaluation of the (a) color, (b) BOD and (c) COD removal levels as a function of
the electrolysis time in an electrochemical cell operating in a hybrid batch-continuous
Given that a continuous operation mode is more suited for mode, shown as during the batch start up period (S1) and the continuous operation
mode (S2) at wastewater feed rates of (>) 4.0, (,) 4.5 and (6) 5.0 ml/min. All cases
actual commercial applications, the continuous operation of the
had a current density of 2.53 mA/cm2, initial wastewater pH and dilution of 11.87 and
electrochemical treatment was performed using the same 50-fold, circulating flow rate of 3.46 l/min and NaCl at 2.0 g/l.
optimum conditions set for the batch operation (current density of
2.53 mA/cm2, wastewater initial pH and dilution level of 11.87 and
50-fold, circulating flow rate of 3.46 l/min and a NaCl concentration presented here the system essentially becomes a continuous one.
of 2.0 g/l). Three feed rates of wastewater to the electrochemical With regards to the effect of the feed rate, the removal efficiency
reactor were then evaluated, namely 4.0, 4.5 and 5 ml/min. decreased as the feed rate increased of feed rate for all pollutants,
However, so as to allow the accumulation of the active reactant but particularly for BOD and COD. Faster wastewater feed rates
species (Hþ/OH/OCl) to near equilibrium levels in the system, the would both reduce the effective residence time (electrolysis time)
treatment process was run as a batch operation for the first 3 h (i.e. and the reactant: pollutant molar ratio and so result in a lower
feed rate of zero) and then as a continuous mode by supplying the probability of collision between the active reactant species and the
indicated federate of fresh wastewater thereafter. All investigated organic and inorganic pollutant compounds. Based on the FTIR
pollutants were almost completely removed during the batch start spectra (Fig. 2(c)), the disappearance of the oxidative coupling unit
up operation (S1) in all cases (Fig. 8). However, when the fresh of lignin (syringyl and guaiacyl units) was still observed in this
wastewater was supplied continuously (S2), a drop in the pollutant experiment, indicating that this process was effective in reducing/
removal efficiency was observed, particularly that for BOD and COD eliminating the organic or inorganic compounds and in particular
removal. This is because the generation rate of the active reactants, lignin.
and so their concentration or reactant: pollutant molar ratio was The characteristics of the wastewater obtained from electro-
not adequate to react with the larger quantity of pollutants entering chemical treatment in the hybrid batch-continuous operation
the system within the short time period the wastewater would be mode at a feed rate of 4 ml/min are summarized in Table 1. The pH
resident in the system. Nevertheless, after 2 h onwards of contin- of the treated wastewater was in the strongly acidic range, but this
uous operation the removal efficiency of COD and BOD increased could be addressed by its neutralization with the basic solution
slowly approaching their steady state conditions after 5e7 h of obtained in the cathodic compartment. All pollutants were mark-
continuous operation. Note that with longer run times that that edly reduced to below the current maximum allowed levels for
406 K. Chanworrawoot, M. Hunsom / Journal of Environmental Management 113 (2012) 399e406
discharge to the environment by the Thai Government, except for
BOD and TDS, which were still 5.0- and 3.3-fold higher, respec-
tively. To further lower the BOD content in the treated wastewater,
the feed rate of wastewater should be reduced. With regards to the
reduction of the TDS levels, suitable post-electrolytic treatment,
such as the use of an ion exchange system, should be evaluated.
3.4. Estimation of the operating cost
A preliminary comparative cost analysis of the pulp and paper
mill wastewater treatment by electrochemical methods was per-
formed considering the operating cost as the cost of chemicals,
electricity and sludge treatment. As demonstrated in Table 2, the
electrochemical treatment in batch mode had a slightly lower
electricity consumption, high additive utilization and large quantity
of sludge production compared with the electrochemical treatment
in the hybrid batch-continuous operation mode. The wastewater
properties obtained from both electrochemical modes were almost
the same except COD and TSS. Based on the level of COD in
wastewater, the electrochemical treatment in the hybrid batch-
continuous mode consumed a slight high operating cost
(2.33 USD/kg COD). However, a continuous operation mode is more
suited for actual commercial applications in pulp and paper mill
industries.
4. Conclusions
The obtained results demonstrated that the electrochemical
method was more effective in terms of both the treatment effi-
ciency and the operating cost. Wastewater dilution, circulating
water flow rate, current density and sodium chloride concentration
affected on the treatment efficiency of all investigated pollutants.
The electrochemical method operating in a batch mode (current
density of 2.53 mA/cm2, circulating flow rate of 3.46 l/min, initial
wastewater pH of 11.87 and dilution of 50-fold and NaCl at 2.0 g/l
for 3 h electrolysis time) gave higher color, BOD and COD removal
levels of 98%, 98% and 97%, respectively. For the hybrid batch-
continuous operation mode, the electrochemical process was
more effective at treating wastewater at a low feed rate. At a feed
rate in the range of 4e5 ml/min, the system reached its steady state
condition within 8 h after start-up (5 h of continuous operation
mode) and achieved a greater than 91%, 83% and 86% reduction in
the color, BOD and COD levels, respectively.
Acknowledgments
The authors thank the Center for Petroleum, Petrochemicals and
Advanced Materials, Chulalongkorn University for facility support,
the Advance agro Public CO., LTD. for samples and materials. We
also thank the Publication Counseling Unit (PCU) of the Faculty of
Science, Chulalongkorn University, and Dr. Robert D.J. Butcher for
comments, suggestions and checking the grammar.
Nomenclature
CE Current efficiency (%)
(COD) t chemical oxygen demand at time t [gO2/l]
(COD)tþDt chemical oxygen demand at time t þ Dt [gO2/l]
F Faraday constant [26.8 Ah]
I Current intensity [A]
L Volume of electrolyte [l]
t Electrolysis time [h]
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