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Treatment of Adsorbable Organic Halide (AOX) from pulp and paper MARK
industry wastewater using aerobic granules in pilot scale SBR
⁎ ⁎
I.H. Farooqi , Farrukh Basheer
Department of Civil Engineering, Z.H. College of Engineering and Technology, A.M.U., Aligarh 202002, India
A R T I C L E I N F O A B S T R A C T
Keywords: Aerobic granulation of activated sludge was achieved in a pilot scale column type sequencing batch reactor
AOX (SBR) employed for the treatment of pulp and paper industry wastewater containing Adsorbable Organic Halide
SBR (AOX) in the range of 15–20 mg/L. Throughout the 780 days of operation the biomass trends to remain in
Aerobic granules between 7 and 8 g/L MLVSS and SVI reduced to 60–80 mL/g MLSS. After applying different selection pressure
Pulp and paper industry wastewater
the average size of aerobic granule in the SBR was in the range of 2–4 mm. After achieving steady state con-
ditions in the pilot plant, at an organic loading rateof 4.5 kg COD m−3day−1 at 6 h HRT the degradation of AOX
was significant and the effluent AOX concentration of below 5 mg/L was achieved. The results achieved in the
study exhibit the viability of formation of aerobic granules in pilot scale SBR and maintenance of long-term
strength of aerobic granular sludge with a high reduction of AOX in pulp and paper industry wastewater.
1. Introduction pulp and paper mill wastewater have bulking problem, which in result
causes poor settling of sludge and effluent have more suspended solids
The pulp and paper industry is a water demanding production and [7,8]. The use of chemicals such as chlorine, hydrogen peroxide, metal
ranks only third in the world, after the primary metals and the chemical ions (Fe, Ca, Mg) are effective in getting better settling properties of
industries, in terms of freshwater consumption [1]. Around 500 diverse sludge in paper mill wastewater treatment [9,10]. Moreover these
chlorinated organic compounds have been identified including chloro- chemical addition methods are not cost effective and they do not pro-
form, chlorate, resin acids, chlorinated hydrocarbons, phenols, ca- vide long term solutions for bulking problem. Conventional adsorption
techols, guaiacols, furans, dioxins, syringols, vanillins, etc [2,3]. The technique, post-treatment using a granular activated carbon (GAC) has
discharge of the Halogenated Organic Compounds in the environment is been widely used for removal of AOX from pulp and paper mill was-
increasingly becoming a matter of concern due to their carcinogenic/ tewater. However GAC have to be regularly regenerated, because ad-
toxic effects. Most of these compounds are adsorbable and in waste- sorption site are exhausted by pollutants after some time [11]. Osman
water, these compounds are estimated in a group as “Adsorbable Or- et al. [5]. have used GAC in sequencing batch biofilm reactor (GAC-
ganic Halides” (AOX). SBBR) to treat recycle paper mill wastewater and results showed high
The formation of these compounds is due to the use of chlorine and AOX removal efficiency by maintaining longest hydraulic retention
chlorinated compounds in the various industrial processes including the time (HRT). The advantage of the biofilms in these systems save energy
bleaching process in the pulp and paper industries. The pulp and paper and less area is required, efficient to handle toxicity and can withheld
industries also being one of the major consumers of chlorine and its high organic loading rate [12].
compounds need main concern in the perspective of removal of AOX These days a new technology of aerobic granulation in column type
discharges in their effluents. The toxic effects of AOX (e.g. chlor- Sequential Batch Reactors (SBR) have been widely explored based on
ophenols, guaiacols, furans and dioxins) range from carcinogenic and modified activated sludge process. Due to the excellent settling capacity
mutagenic effects to acute and chronic toxicity and can act as inhibitors of aerobic granules, large area for a settling tank will not be required,
of microorganism growth, [3–5]. Conventional wastewater treatment which in turn reduces the wastewater treatment plant area by 80%
systems such as activated sludge process have been used for treatment [13]. Aerobic granules have unique structure and microorganisms that
of pulp and paper mill wastewater. The process has disadvantage of can withstand high loading rate as well as high toxicant concentration.
excess sludge production and fluctuations in removal efficiency for Aerobic granulation can be considered as a special type of self-ag-
recalcitrant compounds [6]. Activated sludge process for treatment of gregation of microorganism, without any carrier medium for growth of
⁎
Corresponding authors.
E-mail addresses: farooqi_izhar@yahoo.com (I.H. Farooqi), farrukhbasheer@yahoo.com, farrukhbasheer.cv@amu.ac.in (F. Basheer).
http://dx.doi.org/10.1016/j.jwpe.2017.07.005
Received 28 March 2017; Received in revised form 21 June 2017; Accepted 9 July 2017
2214-7144/ © 2017 Elsevier Ltd. All rights reserved.
I.H. Farooqi, F. Basheer Journal of Water Process Engineering 19 (2017) 60–66
biofilms. The immobilization of microbial cells into granule formation (fill, react, settle and decant) in individual cyclic operation is shown in
generally improved the ability of cells inside the granules to tolerate Table 3. Initially settling time was kept at 30 min thereafter selection
high toxicity concentration and achieve good structural properties and load was applied on day 150 as the settling time was reduced from
biodegradation performance. Sequential batch reactors have ad- 30 min to 5 min. This was done to retain the heavier aerobic sludge in
vantages of low operating costs, no secondary clarifier required, no the reactor which helps in formation of dense and compact aerobic
recycling pumps required, and good control over filamentous microbial granules. The reactor run was completed at 6 h of cycle after achieving
growth, tolerance to shock loads and denitrification during anoxic fill a significant reduction in the values of AOX and COD and was operated
and settle phase [14]. Most of the lab scale and pilot scale studies were for a total period of 780 days.
carried out for municipal wastewater treatment using aerobic granu-
lation [15–18] and for synthetic wastes [13,19]. Very few studies have 2.3. Analytical methods
been carried out for development of aerobic granules on actual in-
dustrial wastewater like petrochemical wastewater [20], palm oil mill Measurement of pH, biomass concentration, COD, BOD, Sludge
effluent (POME) [21], Brewery wastewater [22]. However, till date no Volume Index SVI were conducted in accordance with Standard
work has been reported for the treatment of AOX compounds from pulp Methods [23]. COD was measured using Closed Reflux method/Hach
and paper industry using aerobic granulation technology. The present Reagents (DR5000 UV/Vis spectrophotometer, HACH, USA),pH was
work carried out to evaluate the feasibility of a pilot scale SBR for the measured using HQ30d portable meter coupled with pH probe, HACH,
development of aerobic granules and to assess its performance for the USA. Continuous DO was measured using online HACH probe attached
biodegradation of AOX presents in the pulp and paper industry waste- with PLC. Dissolved oxygen concentration (DO) was measured using
water HACH, USA HQ30d portable meter coupled with LBOD10101 probe.
Samples were taken from the reactor at a predetermined time intervals
2. Materials and methods for analysis.
Aerobic Granule was analysed using Cenisco binocular petrological
2.1. Reactor setup and operation microscope with SANYO digital camera. The photographs were ana-
lysed using image analysis (IA) system (Averz Software).The mor-
The Naini Tissue industry, Uttarakhand, India has been chosen for phology of aerobic granules in stipulation to aspect ratio was analysed
the study as it utilises agro based material and chlorine for bleaching by using IA technique. Aspect ratio is the ratio between minor axis and
purpose. The formation of AOX compounds occur when agro based major axis of ellipse corresponding to the granule (0 = line,
materials are used as raw materials and chlorine is used for bleaching. 1 = circle). Granule strength is defined as an integrity coefficient (IC)
The diameter of the pilot scale SBR was 600 mm and the effective (%) which is the residual volatile suspended solids (VSS) after sample
height was 3000 mm resulting in total volume of 3.394 m3 and height has been agitated for 5 min at 200 rpm on a platform shaker to total
to diameter (H/D) ratio of 5:1 (Fig. 1). The Pilot Plant was seeded with VSS of the intact granules prior to agitation [24]. The stronger granules
the aerobic sludge of the aeration tank of the existing effluent treatment have higher ICs.
plant of the industry. Initially a 24 h cycle was maintained and was
strictly followed. Later on the cycle of operation was reduced to 12 h, 2.4. Adsorbable Organic Halide
8 h and 6 h. Programmable Logical Control (PLC) arrangements for the
automation of the Pilot Plant SBR were used. Effluent was withdrawn The AOX measurements were done by Multi X 2500 halide analyzer
from a port located at 40% height from the bottom resulting in volume (Jena, Germany). Nie et al. [25] described the basic method and process
exchange ratio of 60% (2.04 m3).At maximum organic loading rate at as follows: Effluent first passed through the activated carbon column,
HRT of 6 h the working capacity of pilot SBR was 8.16 m3/day of the organic chloride of the bleaching effluent then adsorbed by the
wastewater. activated carbon column. Sodium nitrate was used in washing the ad-
sorbed inorganic chloride of the activated carbon column, and then the
2.2. Acclimatization and development process of aerobic granules activated carbon column burned in the combustion furnace. Content of
AOX calculated though the micro coulomb titration method [25,26].
The pilot plant was seeded with the aerobic sludge of the aeration
tank of the effluent treatment plant of the industry. The reactor was fed 2.5. Gas chromatography–mass spectrometry
with the wastewater of the equalization tank. Diffused aeration was
provided with the help of a blower and special types of diffusers were GC (Gas chromatography) and GC/MS (Gas chromatography–mass
fitted at the bottom of the reactor which prevented the choking with spectrometry) analysis of influent and effluent samples were done in
sludge. Initially a 24 h cycle of operation was maintained which in- order to identify the number of products formed during aerobic bio-
cluded fill react settle and decant timings of respectively. The samples degradation of pulp and paper mill wastewater. GC/MS equipped with
were collected daily and were analysed for pH, alkalinity, Chemical a split/splitless injector and a Perkin Elmer Clarus 680, USA gas chro-
Oxygen Demand (COD), Biochemical Oxygen Demand (BOD), matograph interfaced with a Turbomass spectrometric (Perkin Elmer
Adsorbable Organic Halides (AOX). Provision of online measurement of 600T, USA) mass spectrometric mass selective detector system were
dissolved oxygen was made using online HACH D.O. monitoring used. The samples were prepared and analysed under conditions as
system. The sludge of the reactor was also analysed for its volatile described previously [13]. The metabolic intermediates were derived
content on a routine basis. from degradation of AOX identified by comparing their retention time
In the initial phase the reactor was fed with diluted pulp and paper (minutes) and mass spectra with that of the National Institute of
industry wastewater with sewage (1 in 10) for proper acclimatization Standard and Technology (NIST) library available.
and growth of the microorganism. Thereafter the dilution was reduced
to 1in 5, 1in 4 and 1in 3.sucessfully operating the pilot plant at reduced 2.6. Extracellular polymeric substances
dilution for 220 days of operation wastewater having characteristics
shown in Table 1 was fed to the reactor. The reactor was run on a 24 h The extracellular polymeric substances (EPS) of the flocculent
cycle till a substantial removal of AOX, BOD and COD removal took sludge and aerobic granules were extracted using a heat extraction
place. The cycle of operation was reduced to 12, 8 and 6 h (on day 150, method as described earlier [27]. The carbohydrate content of the ex-
day 300 and day 475) once pseudo steady state conditions were tract was analysed by the phenol-sulphuric method and expressed as
achieved in each stage as shown in Table 2. The duration of each phase the glucose equivalent, and its protein substance content were
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I.H. Farooqi, F. Basheer Journal of Water Process Engineering 19 (2017) 60–66
Fig. 1. (a) Schematic diagram of the pilot-scale SBR. (b) Pilot Scale SBR reactor for cultivating aerobic granules with pulp and paper mill wastewater in Naini Tissue industry,
Uttarakhand, India.
Table 1 Table 3
Charecteristics of Pulp and Paper industry wastewater. Duration of each phase during cyclic operation in SBR.
Parameter Units Range Cycl (hours) Fill (hours) React(Aeration) Settle Decant
(hours) (hours) (hours)
Chemical Oxygen Demand (COD) mg/L 2000–3000
Biochemical Oxygen Demand (BOD) mg/L 600–1350 24 0.25 23 0.5 0.25
Adsorbable Organic Halide (AOX) mg/L 10–22 12 0.25 11.5 0.083 0.167
Total Suspended Solids (TSS) mg/L 2500–4000 8 0.25 7.5 0.083 0.167
pH – 7.5–8.5 6 0.25 5.5 0.083 0.167
Phase 1st 2nd 3rd 4th 3.1. Pilot plant SBR performance
Period. Days 0–150 150–300 300–475 475–800
Cycle Time/HRT Hours 24 12 8 6 Mounteer et al. [28] studied the removal of recalcitrant COD of
COD loading rate kg COD 0.3 2.25 3.45 4.5 bleached Kraft pulp effluents in SBR. Their results suggested that the
m−3day−1 microorganisms in activated sludge were capable of degrading re-
AOX Removal% 60 70 75 79
COD Removal Removal% 80 75 85 88
fractory COD, but were not metabolically active during activated sludge
SVI ml g−1 MLSS−1 120–130 110 75–85 60–70 process treatment of pulp and paper mill effluent. They also suggested
MLVSS g L−1 3–5 5–6.5 6.5–7.5 7–8 the use of biological selector in the treatment process that can enhance
Size of Granules mm – 0.5–1 1–2 2–4 the efficacy of microorganisms to remove refractory compounds. The
Integrity % – – 90 95
Sequencing Batch Reactor operation consisted of cycles of feed, aera-
Coefficient
tion, settling, and decant. The aeration phase is of two stages: biode-
gradation stage in which substrate was degraded to lowest level, fol-
lowed by the second stage of food scarcity in which no food was
available. The feast and scarcity periods in one cycle are the typical
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I.H. Farooqi, F. Basheer Journal of Water Process Engineering 19 (2017) 60–66
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I.H. Farooqi, F. Basheer Journal of Water Process Engineering 19 (2017) 60–66
Table 4
Different compounds identified in the pulp and paper mill wastewater in GCe MS
Analysis.
1. Phenol 2 methoxy
2. 4h-pyran-4-one, 2,3-dihydro-3,5 dihydroxy-6 methyl
3. 2 methoxy phenol
4. Benzene, 1,4-dimethoxy
5. Phenol 2 methoxy-4 methyl
6. 3 methyl phenol
7. 4 vinylguaiacol
8. 3 methoxy 5 methyl phenol
9. Phenol 3,4-dimethoxy
Fig. 5. The variation of influent and effluent AOX with time. 10. Phenol 2,6 dimethoxy
11. 4 chloro, 2,5 xylenol
12. Benzene, methyl (1-methyl ethyl)
washed out in the initial period of acclimatization indicating the ac- 13. Pentanoic acid
cumulation of granules, and 94 and 95% of the total 2, 4-Di- 14. Phenol 2,6-dimethoxy-4-(2propenyl)
chlorophenol and COD removal efficiencies were achieved respectively. 15. Pentalchlorophenol
16. 2,2-bis(4Hydroxyphenyl) propane
17. Cedrol
3.3. Development of aerobic granules 18. 2,6 Diisopropylphenol
Fig. 6. Chromatographic analysis of pulp and paper industry wastewater. (a) influent and (b) effluent.
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I.H. Farooqi, F. Basheer Journal of Water Process Engineering 19 (2017) 60–66
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