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Bioresource Technology 99 (2008) 7383–7387

Short Communication

Paper and board mill effluent treatment with the combined


biological–coagulation–filtration pilot scale reactor
Muhammad Afzal, Ghulam Shabir, Irshad Hussain, Zafar M. Khalid *
Environmental Biotechnology Division, National Institute for Biotechnology and Genetic Engineering (NIBGE), P.O. Box 577, Faisalabad, Pakistan

Received 4 October 2007; received in revised form 16 January 2008; accepted 20 January 2008
Available online 17 March 2008

Abstract

Pilot scale reactor based on combined biological–coagulation–filtration treatments was designed and evaluated for the treatment of
effluent from a paper and board mill. Biological treatment by fed batch reactor (FBR) followed by coagulation and sand filtration (SF)
resulted in a total COD and BOD reduction of 93% and 96.5%, respectively. A significant reduction in both COD (90%) and BOD (92%)
was also observed by sequencing batch reactor (SBR) process followed by coagulation and filtration. Untreated effluent was found to be
toxic, whereas the treated effluents by either of the above two processes were found to be non-toxic when exposed to the fish for 72 h. The
resultant effluent from FBR-coagulation–sand filtration system meets National Environmental Quality Standards (NEQS) of Pakistan
and can be discharged into the environment without any risks.
Ó 2008 Published by Elsevier Ltd.

Keywords: Biodegradation; Fed batch reactor; Paper and board mill effluent; Sequencing batch reactor; Wastewater treatment

1. Introduction effluent such as those based on aerobic, anaerobic, algal,


fungal biomass, ozonation, electrochemical, photocataly-
The pulp and paper industry is the second largest indus- sis, coagulation–flocculation treatment (Tarlan et al.,
try after textile in Pakistan, with 140 plants employing 2002; Gonzalez et al., 2003; Belmonte et al., 2006; Buzzini
about 85,000 people. Indigenous wheat straw, kahi grass and Pires, 2007; Malaviya and Rathore, 2007; Nair et al.,
and bagasse are used as raw materials in addition to recy- 2007; Ma et al., 2007; Rodrigues et al., 2008).
clable waste in most of the paper industries of Pakistan. Sequencing batch reactor (SBR) is a fill-and-draw acti-
The Pakistani pulp/paper industry consumes large volumes vated sludge system for wastewater treatment (Dubeski
of water (60 m3/tonne of paper produced) and energy. et al., 2001; Wilderer et al., 2001). In this system, waste-
Since the pulp produced corresponds to about 40–45% of water is added to a single ‘‘batch” reactor, treated to
the original weight of raw material, the effluents are heavily remove undesirable components, and then discharged.
loaded with organic matter, having high suspended solids, This method has also been proved effective for pulp and
color, COD and BOD. Most of the Pakistani paper/pulp paper industrial wastewater treatment (Tsang et al.,
mills do not have satisfactory and adequate wastewater 2007). The fed batch reactor (FBR), however, is relatively
treatment facilities and are thus a cause of serious environ- a new concept in wastewater treatment technology
mental concern (Qureshi, 2003). (Moreno-Andrade et al., 2006). It involves the slow addi-
Worldwide, there are many existing biological and tion of highly concentrated wastewater (or nutrient med-
chemical treatment processes for paper and board mill ium) into an aeration tank/reactor with no effluent
removal until the tank is full. Although the FBR process
*
Corresponding author. Tel.: +92 41 2651475; fax: +92 41 2651472.
is quite effective in fermentation/bioprocessing industry
E-mail addresses: afzal@nibge.org (M. Afzal), zafarkhalid@nibge.org but it is still under-explored for paper mill effluent
(Z.M. Khalid). treatment.

0960-8524/$ - see front matter Ó 2008 Published by Elsevier Ltd.


doi:10.1016/j.biortech.2008.01.046
7384 M. Afzal et al. / Bioresource Technology 99 (2008) 7383–7387

It is obvious that a wastewater treatment process based 2.4. Operational conditions


on a single biological, chemical or a physical approach is
not effective enough to meet the increasingly stringent dis- The following operating parameters were maintained
charge requirements of paper/pulp industries (Thompson during the biological–coagulation–filtration treatment of
et al., 2001). In view of these problems, the primary objec- wastewater: 20 min filling period for SBR operation and
tive of this study was to design and evaluate a combined 10 h for FBR operation, 30 h for aeration, 30 min for each
biological, coagulation and filtration treatment process at of settling, clarified liquid removal, coagulation and sand
pilot scale to find an economical and equally effective filtration. Other operational parameters were; hydraulic
strategy to treat wastewater streams from paper/pulp retention time (HRT) 0.5 and 15 h, volumetric loading rate
industries, which could in fact be adopted by small scale (VLR) 6000 and 200 mg L1 h1, respectively, for SBR and
paper/pulp industries in developing countries like FBR. Sludge retention time (SRT) was approximately 5–
Pakistan. 10 days, mixed liquor suspended solids (MLSS) concentra-
tion between 4500 and 5000 mg L1 and sludge volume
2. Methods index (SVI) 50.4 mg L1 for both SBR and FBR.

2.1. Wastewater collection and characterization 2.5. Biological treatment of wastewater by SBR and FBR

The dissolved air flotation (DAF) treated paper and For SBR treatment, 200 L of wastewater was fed to the
board wastewater (PBW) used in this study was collected biological reactor with or without required nutrients (N
from main outlet of Century Paper and Board Mill located and P), and inoculated with activated sludge. Nutrients in
in Kasur, Pakistan and analyzed for various physico-chem- the form of Urea and di-ammonium hydrogen phosphate
ical parameters such as pH, EC, TDS, TSS, settleable sol- were supplied to maintain a BOD:N:P ratio of 100:5:1.
ids, N, P, COD, BOD, and phenol contents using standard Supplementary trace minerals were added into the waste-
methods (APHA, 1998). water before each treatment as described by Chua (1998).
Before feeding to the reactor, temperature of the wastewa-
ter was brought to room temperature. Temperature, pH
2.2. Activated sludge enrichment and the dissolved oxygen of the wastewater during opera-
tion were 30 ± 2 °C, 7.0 ± 1 and 3 ± 0.5 mg L1, respec-
The activated sludge, used as inoculum, was collected tively. Samples collected after every 4 h for 24 h were
from the return sludge of local municipal sewage treatment analyzed for COD and BOD. In case of FBR process,
plant. This activated sludge was enriched by growing it in a about 10 L of wastewater (50% diluted with tap water)
glass reactor (5 L capacity) containing diluted wastewater. was placed in the biological reactor in the presence/absence
The concentration of wastewater was increased gradually of required N and P, and inoculated with 1 L activated
to screen and isolate highly adopted bacterial strains which sludge. The reactor was aerated for two days to obtain a
could survive and grow in the presence of PBW. The dense culture. After two days, continuous feeding of the
adopted enriched bacterial strains formed flocs which ulti- wastewater was started without any effluent removal. Tem-
mately settled down and supernatant was removed to get perature, pH and dissolved oxygen of the wastewater dur-
concentrated activated sludge. The resulting activated ing operation were almost same as in SBR operation. The
sludge was then used as inoculum in SBR and FBR for reactor liquid volume increased linearly with time at a rate
the biological treatment of PBW. of 20 L h1.

2.3. Pilot scale reactor 2.6. Coagulation and sand filtration

A pilot scale reactor consisted of a wastewater storage Biological treated wastewater by SBR and FBR opera-
tank, biological reactor for SBR and FBR operation, tions was left for 30 min for the settling of activated sludge
alum treatment tank and sand filtration tank. Biological (microorganisms, non-biodegradable materials). After set-
reactor was made of glass container with a working vol- tling, wastewater pumped into coagulation tank was mixed
ume of about 200 L and covered with a stainless steel thoroughly with alum powder (150 mg L1 of wastewater)
lid having options for air supply and temperature/pH for about 30 min at 120 rpm with an electric motor and
probes. Sand filtration tank was a glass container with a allowed to settle down again for 30 min. The supernatant
sand bed of 3 in. thickness at the bottom. Coagulation was passed through the freshly prepared sand bed under
treatment tank was a plastic container. Filling and with- the force of gravity to remove the suspended particles.
drawing of wastewater was carried out by peristaltic After each filtration of 200 L biological and chemical trea-
pumps and mixing in biological and coagulation tank ted wastewater, sand was cleaned by soaking in diluted sul-
was done by overhead motor stirrers with stainless steel furic acid for overnight, then washing with tap water, and
paddles (120 rpm). Air was purged in the biological tank finally washing and soaking in distilled water. This sand
by an air compressor. was dried at 150 °C and reused for filtration.
M. Afzal et al. / Bioresource Technology 99 (2008) 7383–7387 7385

2.7. Biotoxicity assay cantly higher than most of the previous reports (Dubeski
et al., 2001; Tarlan et al., 2002; Gonzalez et al., 2003; Buzz-
Acute toxicity of treated and untreated wastewater was ini and Pires, 2007; Malaviya and Rathore, 2007; Nair
determined by exposing fish (Labeo rohita) to the wastewa- et al., 2007) with comparable initial values of COD and
ter (APHA, 1998). The average weight and length of 4.5 BOD. Addition of N and P during biological treatment
months old fish was 1.6 ± 0.3 g and 5 ± 1 cm, respectively. (SBR and FBR) further improved COD and BOD reduc-
Before testing toxicity of each sample, pH of the wastewater tion by 8–11% and 16–20%. These observations are in close
was adjusted to 7 ± 0.5 with HCl/NaOH and then passed agreement with other’s findings (Shabir et al., 2008; Niko-
through the sand bed. The wastewater was then placed in lopoulou et al., 2007) who reported enhanced biodegrada-
water bath to bring its temperature to 22 °C. For each treat- tion by the addition of nutrient mineral fertilizers along
ment, five fish were transferred to aerated aquaria contain- with the bacterial inocula.
ing 10 L tap water (control), treated and untreated
wastewater in triplicate. The mortality data of fish were 3.3. Tertiary treatment
recorded for 72 h. As per requirement of the test, no feed
was supplied to the experimental fish; the aeration however When PBW treated by SBR operation on pilot scale was
was supplied continuously till the end of experiment. Dead further treated with alum, after settling and filtration, an
fish, if any, were immediately removed from each tank. additional 41.37% COD and 17.12% BOD reduction was
observed, which resulted in total COD and BOD reduction
3. Results and discussion of 90.48% and 92.27%, respectively. Similarly 37.93% and
17.99% improvement in the reduction of COD and BOD,
3.1. Effluent characterization respectively, was observed after subjecting FBR treated
wastewater with alum followed by settling and filtration
Physico-chemical characterization of paper and board (Table 1). These results indicate that the effluent quality
mill effluent (DAF treated) showed that it contained was significantly improved by removing organic/inorganic
(mg L1) BOD 488 ± 19, COD 2054 ± 21, TDS 2873 ± materials by biodegradation followed by the coagulation
42, TSS 145 ± 13, phenol 2.19 ± 0.12, nitrogen 2.15 ± and filtration. This combined treatment strategy can thus
0.25, phosphorous 1.2 ± 0.13; pH 6.6, EC (mS cm1) have better potential to treat less biodegradable effluent
2.18 ± 0.01 and settleable solids (ml L1) 0.71 ± 0.03 (all over single-step treatment methods alone (Ma et al.,
results mean of three replicates). Due to higher values of 2007; Rodrigues et al., 2008). Dewatered alum sludge
BOD, COD and phenol, the effluent did not comply with formed during coagulation of biological treated wastewater
the permissible National Environmental Quality Standards can further be used for the removal of lead (Chu, 1999) and
(NEQS, 1999). other contaminates from the water and wastewater (Yang
et al., 2006). However, some of the residues formed may
be hazardous to aquatic environment. Therefore biotoxic-
3.2. Performance of SBR and FBR operations
ity experiments were also performed.
By biological treatment of PBW on pilot scale, 49% and
55% COD, and 75% and 78% BOD was reduced by SBR 3.4. Biotoxicity
(data not shown) and FBR (Fig. 1) processes, respectively,
within 24 h in the presence of N and P, which is signifi- After treatment of PBW on pilot scale, actute toxicity
was completely removed. Fish exposed to untreated PBW

Table 1
COD and BOD reduction in paper and board mill wastewater by pilot
scale reactor
Treatments COD Total BOD Total
(mg L1) removal (%) (mg L1) removal (%)
SBR operation
Inlet PBW 1975±85 0.0 479±51 0.0
After BT (24 h) 1005±34 49.11 119±21 75.15
After CT + SF 188±17 90.48 37±3 92.27
FBR operation
Inlet PBW 1960±95 0.0 456±4 0.0
After BT (24 h) 880±51 55.10 98±13 78.50
After CT + SF 136±16 93.03 16±4 96.49
Each value is a mean of three treatments and ± indicates variation among
Fig. 1. COD and BOD reduction in PBW by FBR operation on pilot scale them.
in the presence (N, d) and absence (4, s) of additional nitrogen and CT = coagulation treatment; SF = sand filtration; BT = biological treat-
phosphorous. Error bars indicate standard error among three replicates. ment; PBW = paper and board wastewater.
7386 M. Afzal et al. / Bioresource Technology 99 (2008) 7383–7387

Table 2
Mortality of fish at different concentration of untreated and treated paper and board mill wastewater
12 h 24 h 48 h 72 h
Concentrations Dead Alive Dead Alive Dead Alive Dead Alive
Water control 0 5 0 5 0 5 0 5
Untreated PBW
Undiluted 5 0 – – – – – –
50% diluted 0 5 0 5 0 5 2 3
25% diluted 0 5 0 5 0 5 1 4
Treated PBW
Undiluted 0 5 0 5 0 5 0 5
PBW = paper and board wastewater.

(undiluted) died immediately, while 50% and 25% diluted ECF bleached kraft mill effluent due to biomass adaptation. J. Hazard.
untreated PBW caused death of two and one fish out of five Mater. 135 (1–3), 256–263.
Buzzini, A.P., Pires, E.C., 2007. Evaluation of a upflow anaerobic sludge
after 72 h, respectively. Many authors reported the lethal blanket reactor with partial recirculation of effluent used to treat
effects on the fish exposed to pulp and paper mill wastewa- wastewaters from pulp and paper plants. Bioresour. Technol. 98,
ter (Pokhrel and Viraraghavan, 2004). Whereas fish were 1838–1848.
remained alive after 72 h when exposed to undiluted trea- Chu, W., 1999. Lead metal removal by recycled alum sludge. Water Res.
ted PBW in our experiments. Thus combined treatment 33 (13), 3019–3025.
Chua, H., 1998. Effects of trace chromium on organic adsorption capacity
of PBW resulted in its detoxification indicating that not and organic removal in activated sludge. Sci. Total Environ. 214, 239–
only original toxicity was removed but metabolites pro- 245.
duced also had no toxic effect. These results are shown in Dubeski, C.V., Branion, R.M., Lo, K.V., 2001. Biological treatment of
Table 2. pulp mill wastewater using sequencing batch reactors. J. Environ. Sci.
These results indicate that the combined biological– Health 36 (7), 1245–1255.
Gonzalez, P., Zaror, C., Carrasco, V., Mondaca, M.A., Mansilla, H.,
coagulation and filtration method investigated to treat pulp 2003. Combined physical–chemical and biological treatment of poorly
and paper mill effluent may effectively be used to reduce bio-degradable industrial effluents. J. Environ. Sci. Health 38 (10),
water toxicity and its pollution load. 2201–2208.
Ma, H., Wang, B., Wang, Y., 2007. Application of molybdenum and
phosphate modified kaolin in electrochemical treatment of paper mill
4. Conclusion wastewater. J. Hazard. Mater. 145, 417–423.
Malaviya, P., Rathore, V.S., 2007. Bioremediation of pulp and paper mill
By FBR-coagulation–filtration reactor, COD and BOD effluent by a novel fungal consortium isolated from polluted soil.
of PBW were reduced to 136 and 16 mg L1, respectively, Bioresour. Technol. 98, 3647–3651.
Moreno-Andrade, I., Buitron, G.N., Betancur, M.J., Moreno, J.A., 2006.
which were below the industrial wastewater discharge stan- Optimal degradation of inhibitory wastewater in a fed batch bioreac-
dards of Pakistan. However, COD and BOD of PBW were tor. J. Chem. Technol. Biotechnol. 81 (4), 713–720.
reduced to 188 and 37 mg L1, respectively, by SBR-coag- Nair, I.C., Jayachandran, K., Shashidhar, S., 2007. Treatment of paper
ulation–filtration reactor. The FBR process was, however, factory effluent using a phenol degrading Alcaligenes sp. under free and
more efficient that SBR to reduce COD and BOD after immobilized conditions. Bioresour. Technol. 98, 714–716.
NEQS (National Environmental Quality Standards) Revised, 1999. The
alum treatment and filtration. Both of these processes ren- Gazette of Pakistan, Extraordinary, Published by Authority, Islama-
dered the effluent non-toxic which though was originally bad, Part II, Statutory Notification (SRO), Government of Pakistan;
toxic. The pilot scale application of the combined treat- Environmental and Urban Affairs Division (Pakistan Environmental
ments to pulp and paper industry effluents exhibit promis- Protection Agency).
ing large-scale perspective. Nikolopoulou, M., Pasadakis, N., Kalogerakis, N., 2007. Enhanced
bioremediation of crude oil utilizing lipophilic fertilizers. Desalination
211, 286–295.
Acknowledgement Pokhrel, D., Viraraghavan, T., 2004. Treatment of pulp and paper mill
wastewater – a review. Sci. Total Environ. 333, 37–58.
Qureshi, M.I., 2003. Pakistan pulp and paper industry. The Environ.
The authors wish to thank the Century Paper and Board Monit. 3 (10), 5–6.
Mill Kasur, Pakistan for providing financial support for Rodrigues, A.C., Boroski, M., Shimada, N.S., Garcia, J.C., Nozaki, J.,
this work. Hioka, N., 2008. Treatment of paper pulp and paper mill wastewater
by coagulation–flocculation followed by heterogeneous photocatalysis.
J. Photochem. Photobiol. A 194, 1–10.
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