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 2563 Q IWA Publishing 2010 Water Science & Technology—WST | 61.10 | 2010

Treatment of wastewater from a low-temperature

carbonization process industry through biological and
chemical oxidation processes for recycle/reuse: a case study
R. Biswas, S. Bagchi, C. Urewar, D. Gupta and T. Nandy

ABSTRACT

Low-temperature carbonization (LTC) of coal generates highly complex wastewater warranting R. Biswas (corresponding author)
S. Bagchi
stringent treatment. Developing a techno-economically viable treatment facility for such C. Urewar
D. Gupta
wastewaters is a challenging task. The paper discusses a case study pertaining to an existing
T. Nandy
non-performing effluent treatment plant (ETP). The existing ETP comprising an ammonia stripper National Environmental Engineering Research
Institute (Council of Scientific and Industrial
followed by a single stage biological oxidation was unable to treat 1,050 m3/d of effluent as per Research),
Nagpur 440 020,
the stipulated discharge norms. The treated effluent from the existing ETP was characterized with India
E-mail: ra_biswas@[Link];
high concentrations of ammonia (75 –345 mg N/l), COD (313–1,422 mg/l) and cyanide (0.5–4 mg/l). samikbagchi@[Link];
Studies were undertaken to facilitate recycling/reuse of the treated effluent within the plant. [Link]@[Link];
[Link]@[Link];
A second stage biooxidation process was investigated at pilot scale for the treatment of the t_nandy@[Link]

effluent from the ETP. This was further subjected to tertiary treatment with 0.5% dose of 4%
hypochlorite which resulted in effluent with pH: 6.6–6.8, COD: 73–121 mg/l, and BOD5: , 10 mg/l.
Phenol, cyanide and ammonia were below detectable limits and the colourless effluent was
suitable for recycle and reuse. Thus, a modified treatment scheme comprising ammonia pre-
stripping followed by two-stage biooxidation process and a chemical oxidation step with
hypochlorite at tertiary stage was proposed for recycle/reuse of LTC wastewater.
Key words | ammonia, coal carbonization, pilot plant, recycle/reuse, two-stage biooxidation
process

INTRODUCTION

Low-temperature carbonization of coal generates coke chemical coagulation, ion exchange and active carbon
wastewater from the ammonia scrubbing process. Coke adsorption (Ghose 2002; Ghose et al. 2006). However, they
wastewater is a complex industrial effluent containing high are accompanied by the high cost of sludge treatment,
concentrations of toxic and refractory compounds such as disposal and activated carbon regeneration (Sarfaraz et al.
tar, phenols, naphthalene, light oil, sulphur-containing 2004). More recently, two stage and three stage biological
organic compounds, cyanide (CN2), thiocyanate (SCN2) treatments comprising various combinations of anaerobic,
and high concentrations of ammonium nitrogen (NHþ
4 -N) anoxic and aerobic configurations are being applied to
and chlorides (Wanmmer 1994; Wong-Chong 1994). It also reduce the pollutant load in treatment of coke wastewater
contains polyaromatic hydrocarbons and heterocyclic (Vazquez et al. 2006b, 2007). These systems are effective and
nitrogenous compounds in low concentration (Vázquez efficient for treating biodegradable wastewaters, and ensure
et al. 2006a; Maranon et al. 2008). Traditionally, expensive good process control (Metcalf & Eddy 2003).
processes have been employed for treatment of coke This article presents a case study on a non-performing
wastewaters, such as steam stripping (Vazquez et al. 2007), effluent treatment plant (ETP) of a LTC industry. The ETP
doi: 10.2166/wst.2010.181
 2564 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

in the present industry comprised of an ammonia stripper Treatment of LTC effluent-existing facility
followed by single stage extended aeration system. Based on
The ETP comprises ammonia stripper, equalization basin
the performance of the existing ETP, extensive R&D studies
(EB), twin aeration tanks (AT), secondary clarifier, polish-
were carried out on laboratory scale. The results of two-
ing lagoon and sludge drying beds. Combined wastewater
stage biooxidation studies at laboratory scale were demon-
from collection tanks were pumped into EB for equalization
strated under field conditions at pilot scale. The aim of this
of flow and characteristics. The equalized effluent was then
work was to design a modified treatment scheme for a non-
pumped to the twin aeration tanks. The mixed liquor from
performing ETP in a LTC plant for zero effluent discharge.
the AT flows through gravity to the clarifier. The clarified
effluent is routed to polishing lagoon before final discharge.
The schematic of the existing ETP is shown in Figure 1.
MATERIALS AND METHODS

The industry Performance assessment of existing ETP

The study was carried out for an LTC industry located in The performance assessment of the existing treatment plant

Eastern India. It produces smokeless processed fuels in was conducted in nineteen full scale monitorings. The study

solid (coke), liquid (tar), and gaseous (coal gas) forms, included hourly flow monitoring, collection of wastewater

through low-temperature carbonization of coal. The other samples at various stages of treatment, and characterization

finished by-products include phenol, xylenol, and cresols. of the composite samples collected over a period of

The manufacturing unit chiefly comprised material 24 hours. The locations of sampling points and the

handling plant, Retort House (RH), Producer Gas Plant characteristics of the samples collected at various locations

(PGP), Gas Cleaning Plant (GCP), Tar Distillation Plant are indicated in Figure 1.

(TDP) and utility. Amongst these units, the Retort House

formed the heart of the manufacturing process. Carboniz- Treatability studies
ation of coal to coke is carried out in the Retort House at
Various bench scale treatability studies were carried out
1,3008C using producer gas. Producer gas is a combustible
with the effluent from the secondary clarifier to make the
mixture of nitrogen, carbon monoxide, and hydrogen,
treated effluent suitable for recycle and reuse. These
generated by passing air with steam over burning coal in a
included both biological and physicochemical studies.
furnace and used as fuel. The raw coal gas having
approximate composition (v/v) of 48% water, 50% tar,
0.3% total ammonia, 0.74% naphthalene, 0.01% H2S, Bio-oxidation studies
0.013% HCN, and heavy metals in traces, is subjected to
The clarifier effluent from the existing ETP was studied for
cleaning and condensation to yield the finished product.
biological ammonia oxidation in a stage II biooxidation
unit. Biomass from the existing activated sludge process was
acclimatized for ammonia oxidation and residual COD
Wastewater generation
removal from the clarifier effluent. Initial experiments were
The tar distillation plant housing the solvent recovery unit started with a 5 liter bench scale unit made up of perspex
3
generates around 50 m /d of process effluent. The run offs sheet. The 5 liter reactor was seeded with the sludge having
from all other units including water from floor washings and an initial TSS of 5 –7 g/l with 95% volatile fraction. One
sanitary sewage are pooled together in a large collection third of the reactor’s capacity was filled with effluent from
tank (CT). Around, 1,000 m3 of wastewater are collected in the existing full-scale biological unit. Initially the effluent
this tank every day and sent for treatment along with the was diluted using domestic sewage so as to maintain the
process effluent. The total quantity of wastewater generated ammonia concentration ,100 mg N/l. The pH was main-
is 1,050 m3/d. tained in the range of 6.8– 7.3 and 1 g/l of NaHCO3 was
 2565
R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry
pH : 6.0–9.8 pH : 6.5–9.1 pH : 6.7–8.1
COD (mg/l) : 204–5,800 COD (mg/l) : 1,040–5,850 COD (mg/l) : 313–1,422
BOD (mg/l) : 87–3,890 BOD (mg/l) : 750–4,550 BOD (mg/l) : 5–575
Phenol (mg/l) : 8–600 Phenol (mg/l) : 75–1,000 Phenol (mg/l) : BDL-2
Cyanide (mg/l) : 0.3–260 Cyanide (mg/l) : 24–210 Cyanide (mg/l) : BDL-4
NH3-N (mg/l) :13.6–919 NH3-N (mg/l) : 98–623 NH3-N (mg/l) : 75–345
Ammonia liquor from TDP
Domestic sewage, effluent
from GCP, TDP, Retort,

1
NH3
4
P
Scrubbed in P
3 5 6 Discharge
H2SO4

4
P
P
Steam 2
NH3 stripper 7

Statutory board standards for pH : 8.0–9.2 1 - Process run-offs collection tank

discharge on to inland surface water COD (mg/l) : 9,312–31,550 2 - Raw effluent collection tank
pH : 5–9 BOD (mg/l) : 980–17,820 3 - Equalization basin
COD (mg/l) : 250 Phenol (mg/l) : 1,050–2,818 4 - Aeration tanks

Water Science & Technology—WST | 61.10 | 2010

BOD (mg/l) : 30 Cyanide (mg/l) : 540–1,700 5 - Secondary clarifier
Phenol (mg/l) :5 NH3-N (mg/l) : 462–2,967 6 - Lagoon pit
Cyanide (mg/l) : 0.2 7 - Sludge drying bed
NH3-N (mg/l) : 50 P - Pump

The characteristics of effluent streams are indicated in boxes. All values are range of nineteen full scale evaluations; BDL-Below detectable
Limits, sampling points

Figure 1 | Schematics of ETP under existing operating conditions.

 2566 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

added to maintain the alkalinity to ammonia ratio in the

range of 5 – 7. Other nutrients (commercial grade phospho-
ric acid of 45% purity: 0.3 ml/l, MgSO4·7H2O: 0.05 g/l,
CaCO3: 0.02 g/l, and FeSO4·7H2O: 0.02 g /l) were also
added to enhance biological activity. Diffused aeration
was provided for aeration and mixing the contents of the
bioreactor. The reactor was batch fed initially. As the
reactor achieved stability, the volume was increased to
5 liters. The reactor was switched to continuous mode of
operation after 15 days of batch operation at a flow rate of
1 l/d. The performance of the stage II unit was optimized
under varying hydraulic retention times (HRT). HRT and Figure 2 | Schematic of pilot plant state II biological unit.

average concentration of the different pollutants in the feed

for the stage II biological unit under different experimental
tank served as inlet reservoir, while another 100 l tank
conditions are presented in Table 1.
served as outlet tank cum settler. Influent (feed) to the
After initial laboratory scale trials in the 5 l reactor, the
second stage bio-oxidation tank was stored in the overhead
effective volume was scaled up to 20 l at a bench scale and
reservoir after pH and alkalinity corrections. The pH of the
then to 200 l at a pilot scale. Through out the experiment,
feed was adjusted at 6.8– 7.2 using commercial grade
the bulk DO concentration in the reactor was maintained at (45% v/v) phosphoric acid. Addition of phosphoric acid
2 ^ 0.5 mg/l. Since the experiments were carried out under also supplemented phosphorus concentration in the feed.
ambient conditions, the liquid temperatures in any of the Sodium bicarbonate was added in the feed to maintain
reactors were not controlled. The liquid temperatures in alkalinity to ammonia ratio in the range of 5– 7 for
the reactors varied from 18– 228C in winter, to 25 – 288C in biological nitrification. The flow of 67 l/d from the over
summer. The sludge age in the 5 l, 20 l and 200 l reactors, head tank to the pilot reactor was regulated through a
was maintained between 35 – 45 days. High SRT was metering pump. Aeration and mixing in the pilot plant was
essential for maintaining very slow growing nitrifying achieved through diffused aeration. The settled biomass
bacteria in the stage II unit. from the 100 l settler was manually recycled back to the
The 200 l pilot plant installed at site was made of a reactor.
cylindrical polystyrene tank. Figure 2 presents a schematic
of the stage II biooxidation pilot plant. A 100 liter over head
Physico-chemical treatability studies
Table 1 | Experimental conditions for operation of stage II bio-oxidation unit
Treatability studies were carried out using effluent from the
HRT Flow rates NH3 COD Phenols
second stage bio-oxidation tank for rendering a recyclable
Scale (days) (l/d) pH (mg N/l) (mg/l) (mg/l)
effluent quality. Experiments were carried out in 1,000 ml
5l 2 2.5 6.8 – 7.3 80 ^ 20 300 ^ 50 ,5
glass beakers containing 500 ml sample in a jar test
3 1.67 6.8 – 7.3 80 ^ 20 300 ^ 50 ,5
apparatus using (i) commercial grade lime and alum as
4 1.25 6.8 – 7.3 80 ^ 20 300 ^ 50 ,5
coagulants and (ii) commercial grade sodium hypochlorite
5 1.0 6.8 – 7.3 80 ^ 20 300 ^ 50 ,5
containing 4% free chlorine as oxidizing agent. The dosage
20 l 3 6.67 6.6 – 6.9 135 ^ 50 315 ^ 50 ,5
of the coagulants and oxidizing agent were varied to
200 l 3 67 6.6 – 6.9 135 ^ 25 315 ^ 50 ,5
establish the optimal dose. The doses (mg/l) of commercial
3 67 6.6 – 6.9 150 ^ 25 350 ^ 50 ,5
grade alum were varied as 250, 500, 750 and 875 along with
3 67 6.6 – 6.9 200 ^ 20 365 ^ 55 ,5
a fixed dose of lime (500 mg/l). In experiments with 4%
3 67 6.6 – 6.9 300 ^ 50 380 ^ 70 ,5
sodium hypochlorite, the dose (v/v) was varied as 0.13,
 2567 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

0.25, 0.38, 0.5, 1, 1.5 and 2.5%. The protocol followed in all DO, cyanide and pH were measured using WTW probes.
the experiments is as follows: coagulation speed: 100 rpm, All data are presented as mean value of measurements made
coagulation time: 1 min, flocculation speed: 10 rpm, floccu- on three replicate samples.
lation time: 30 min, and settling time: 30 min. A control
having no addition of chemicals was set with every
experimental run. All the experiments were carried out in RESULTS AND DISCUSSION
triplicates to confirm the results.
Adequacy assessment of existing ETP

The performance of the ETP with respect to major

Analytical methods
parameters, under the existing operating conditions, is
The parameters like COD (open reflux method), BOD5 shown in Table 2. The characteristics of the treated effluent
(Winkers modification), colour and alkalinity were esti- indicated that existing ETP did not comply with the
mated as per Standard Methods (APHA 1998). Phenol and stipulated norms for discharge into Inland Surface Waters
ammonia were estimated by colorimetric method according with respect COD, BOD, cyanide and ammonia parameters.
to the Standard Methods (APHA 1998). Nitrate, nitrite and Wide variations in feed concentrations in terms of
phosphates were analyzed by an Ion Chromatography COD, phenol, ammonia and cyanide were observed
system (Metrohm make) using conductivity detection (Figure 3). Moreover, the concentration of ammonia in
(APHA 1998). Separation and elution of anions were carried the process effluent was high (1,100 to 2,225 mg/l) and
out in an IonPac A 250A anion column, utilizing carbona- fluctuating. This was in spite of an operational ammonia
te/bicarbonate eluent and auto suppressor technology. The stripper prior to the ETP. High concentration of ammonia
samples from equalized effluent, existing clarifier effluent poses the risk of inhibiting the downstream biological
and effluent from stage II biooxidation unit were scanned oxidation processes (Kwon et al. 2002).
from 200 to 700 nm in a UV-visible spectrophotometer The average ratios of carbon, nitrogen & phosphorus
(Shimadzu UV-1650PC, Japan) using a pair of quartz (C: N: P) in the feed to the aeration tank were 108: 12: 1.
cuvettes for qualitative analysis of biological treatment. This indicated deficiency in phosphate concentration

Table 2 | Performance of ETP under existing operating condition

Performance evaluation during nineteen full scale monitorings

Concentration in
equalized effluent Concentration in treated effluent Percent efficiency
Statutory standards for
Mean and discharge onto inland
Parametersp Range Mean Range standard deviation Range Mean surface water

pH 6.5 – 9.1 8.5 ^ 0.3 6.5 – 8.1 7.8 ^ 0.3 – – 5.5– 9.0
Alkalinity 233 – 1,075 670 ^ 183 10 – 417 250 ^ 126 NIL – 98 63 ^ 31 –
Suspended solids 26 – 200 36 ^ 52 61 – 140 102 ^ 21 30 – 51 45 ^ 15 100
COD 1,040 – 5,850 2,360 ^ 1,214 313 – 1,422 476 ^ 243 57 – 93 81 ^ 10 250
BOD 208C,5 d 750 – 4,550 1,300 ^ 844 5 – 575 129 ^ 105 76 – 99 92 ^ 7 30
†
Phenol 75 – 1,000 250 ^ 237 BDL – 2 0.55 ^ 0.5 98 – 100 99.8 ^ 0.2 5
Total NH2
3 -N 98 – 623 660 ^ 180 75 – 345 210 ^ 81 NIL – 71 46 ^ 40 50
Free NH2
3 -N 45 – 413 82 ^ 76 26 – 162 94 ^ 62 NIL – 79 40 ^ 35 5
Cyanide 24 – 210 108 ^ 55 BDL – 4 0.8 ^ 0.75 95 – 100 98.9 ^ 1.3 0.2
Oil & Grease 12 – 93 42 ^ 19 4 – 10 3.5 ^ 9.8 29 – 89 72 ^ 26 10
p
All values are in mg/L, except pH.
†
BDL—below detectable limits.
 2568 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

(Metcalf & Eddy 2003). The DO concentrations in the detectable limits (BDL)– 2 mg/l and cyanide concentrations
aeration tanks were # 1 mg/l, as the aeration tank was ranging from BDL to 4 mg/l, respectively. The sludge had
always covered with 1 –2 feet thick blanket of foam, good settleability with SVI # 100 ml/gm.
submerging a major part of the surface aerators. Tempera- The adequacy assessment of the ETP treating LTC
tures in aeration tanks varied between 22– 268C during the process effluent revealed that ammonia stripping followed
evaluation period. The existing biological process was by single stage biological treatment was inadequate. The
operated with HRT of 3 d and SRT of 4– 5 d and it was performance data indicated that nitrification was not
yielding more than 95% removal efficiency for phenol and occurring in the existing biological system. This is may be
cyanide, at influent phenol and cyanide concentrations of due to the presence of a high concentration of phenol
75 to 1,000 mg/l and 21 to 210 mg/l, respectively. The (75 – 1,000 mg/l), which could be toxic for nitrifiers (Amor
performance with respect to COD and ammonia was found et al. 2005; Maranon et al. 2008). The other factors that
to be varying in the range 57 – 93%, and no removal 2 71%, could inhibit the growth and survival of nitrifying bacteria
respectively (Figure 3). The effluent from this unit had a pH were (i) insufficient DO concentrations in aeration tank
in the range of 6.7– 8.1, and temperature: 21 – 268C, COD: (DO #1 mg/l), and (ii) low alkalinity to ammonia ratio
313– 1,422 mg/l, ammonia: 75 –345 mg N/l, phenol: below (0.96 –3.2) (Li et al. 2003; Li & Zheng 2004; Bagchi et al.
2009). A further reason for the low nitrification rate could
be inhibition by free ammonia (Anthonisen et al. 1976).
100 8,000
At temperatures of 27 – 378C, a pH of 6.5– 9.1, and
Influent COD (mg/l)

80
Removal (%)

6,000 ammonium concentrations of 600 mg N/l, the free ammo-

60
4,000 nia concentration ranges between 1 and more than 100 mg
40
20 2,000 NH3/l. The possible inhibition amongst various commu-
0 0 nities of microbes in the presence of different polluting
Percentage reduction Influent COD (mg/L) compounds may make treatment of LTC effluent difficult in
100 1,200 a single stage biological unit. Though, nitrification has been
Influent phenol (mg/l)

80 1,000 reported in many activated sludge process treating complex

Removal (%)

800
60
600
organic wastewater, the rate of nitrification may be
40
400 insignificant in full scale applications. Therefore the
20 200 possibility of improving the treatment through modification
0 0
Percentage reduction Influent phenol (mg/L)
within the existing biological reactor was ruled out. The
complex nature of the wastewater necessitates a two or
Influent ammonia (mg N/l)

100 800
three stage treatment scheme (Li & Zheng 2004; Vazquez
50
Removal (%)

600
et al. 2006b). Hence, in the present case, a second stage
0 400
biooxidation unit (stage II unit) for removal of ammonia
–50 200
and residual COD from the effluent of existing biological
–100 0 unit was investigated.
Percentage reduction Influent ammonia (mg/l)
Influent cyanide (mg/l)

100 200
80 Stage II biological oxidation
Removal (%)

150
60
100
40
20 50 Bench scale (5 l)
0 0
1 5 10 15 20 25 As a first step, nitrifying biomass was developed through
Percentage cyanide reduction Influent cyanide (mg/l) enrichment technique using biomass from the existing
biological process. From the results of most probable
Figure 3 | Performance of the biological unit in the existing ETP in terms of COD,
phenol, ammonia and cyanide removal. number (MPN) for nitrifying bacteria it was found that
 2569 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

120 scale up, the NaHCO3 dose was maintained on the higher
Influent pH: 6.8–7.3
Influent COD: 300 ± 50 mg/l side by increasing the dosing from 1 g/l to 1.5 g/l ensuring
Percent ammonia oxidation

100
that alkalinity does not becomes a limiting factor for
80 ammonia oxidation. Higher doses of bicarbonate (2.8 g/l
NaHCO3) have been reported by other workers for
60
supporting nitrification in steel plant and coke oven
40 effluents (Ghusain et al. 2002; Vazquez et al. 2007).
Besides this, in order to maintain a favorable nitrifica-
20
tion process in the reactor, and to avoid competition by fast
0 growing heterotrophic bacteria, the pH of the influent was
1 2 3 4 5 6
HRT (days) maintained in the range 6.6– 6.9. The optimal pH range for
the highly active phenol utilizing bacteria is 7.8 –8.2
Figure 4 | Performance of second stage biological unit against function of HRT.
(Amor et al. 2005). Phenol utilizing bacteria can survive in
the biomass was composed of 16% ammonia oxidizing phenol deficient media by oligotrophic metabolism. Hence,
bacteria with a bacterial count of 5– 20 £ 107 CFU/ml. even in the absence of phenolic substrate, these bacteria
After 15 days of batch operation using diluted effluent from could pose severe threat to slow growing autotrophic
the existing biological unit, the reactor was switched into bacteria and other heterotrophic nitrifying bacteria by
continuous mode of operation at ambient temperature. consuming the available nutrients. As a result of pH and
Since, the characteristics of the effluent from the full scale alkalinity correction, the acclimatization period required in
plant varied significantly, it was very difficult to maintain this bioreactor was very short, and the bioreactor was
the fixed loading rate of ammonia. Hence, HRT was chosen scaled up from 5 to 20 l in 60 days. After achieving more
as the operating parameter. than 90% ammonia removal in the 20 l bioreactor, the
Figure 4 presents the average performance of the content was used as seed for further scaling to the 200 l
reactor against varying HRT of 2, 3, 4 and 5 days. The pilot plant.
maximum ammonia removal of 99% was obtained for HRT
of 3 days with minimum concentration of ammonia in the
Pilot scale (200 l)
effluent being 0.2 mg/l. When HRT was increased beyond
3 days, the ammonia oxidation efficiency decreased. This In the third step, the pilot plant was seeded with the 20 l
may be due to cell death because of higher sludge age (SRT). reactor biomass and operated in batch mode with gradual
Various workers have reported a minimum hydraulic increase in working volume starting from 50 l, to 70 l,
residence of 2.5 days to 4 days for more than 70% followed by 100 l, 150 l, 175 l and finally 200 l. During this
nitrification efficiency in coke oven wastewaters (Amor period, the plant was operated in batch mode, by decanting
et al. 2005; Vazquez et al. 2007). Hence, all the up-scale and replenishing 1/3 of its effective volume daily with fresh
experiments were carried out at a HRT of 3 days. MLSS in feed. The ammonia concentration, pH and bicarbonate
the bioreactor was in the range of 1,500 – 2,000 mg/l. Since doses were maintained as described for 20 l reactor.
growth rate of nitrifying bacteria is very low, high SRT of The performance of the pilot plant during the scale up
50 –60 d was maintained to increase MLSS in this reactor. period is presented in Figure 5. During this period, which
lasted for 3 months, the influent ammonia concentration
was maintained in the range of 80 –150 mg N/l.
Bench scale (20 l)
As depicted in Figure 5, continuous mode of operation
In the second step, the content of the 5 l stage II biological was started on 91st day after the pilot plant achieved
unit was transferred to the 20 l capacity unit. The volume stability in terms of ammonia oxidation in the range
was increased in a step wise manner from 5 l to 20 l with 86– 97%. HRT was maintained at 3 d on the basis of lab
increments of 0.5 l every 2 days. For acclimatization during scale trials. Under continuous mode of operation, ammonia
 2570 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

350 200
Start up phase (batch mode) Inlet
Outlet
Percent efficiency 180
300

160
250
140
Ammonia nitrogen (mg/l)

200
120

Removal (%)
150 100

80
100 Continuous mode

60
50
40

0
20
1 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190

–50 0
Days

Figure 5 | Performance of pilot scale second stage biological unit for ammonia oxidation.

oxidation efficiency of 98% was obtained at an influent During the study period of 190 days, the ammonia
ammonia concentration of 200 mg/l. When increasing the concentration in the effluent was less than 40 mg N/l with
influent ammonia concentration to 305 mg/l, the perform- an average concentration of 10 mg/l. The effluent charac-
ance of the plant declined, necessitating that the influent teristics from the second stage biooxidation process are
ammonia concentration should be within 300 mg N/l. presented in Table 3.

Table 3 | The effluent characteristics from the second stage biooxidation process

Feedp to stage II unit Effluent from stage II unit

Statutory board standards for
Sr. No Parameters Range Standard deviation Range Standard deviation discharge of Inland surface water

1. pH 7.5 – 8.4 7.8 ^ 0.3 5.8– 6.5 6.3 ^ 0.3 5.5 – 9

2. Alkalinity 574 – 1,032 650 ^ 550 43– 107.5 75 ^ 25 –
3. NH3-N 222 – 400 350 ^ 75 4 – 12 5.5 ^ 0.5 50
4. NO3-N 7.5 – 21 15.5 ^ 5.5 35– 43 35 ^ 5 50
5. COD 350 – 711 550 ^ 288 93– 224 127 ^ 55 250
6. BOD 27 – 76 55 ^ 20 NIL† – 17.5 7.5 ^ 5 30
‡ ‡ ‡
7. Phenol BDL – 2 1.2 ^ 0.13 BDL BDL 5
8. Cyanide 0.7 – 1.8 0.9 ^ 0.6 BDL‡ – 0.15 BDL‡ 0.2
§
9. TDS 2,005 – 2,156 2,050 ^ 50 1,523 – 2,531 1,750 ^ 250 –
10. Foaming Foaming present – Negligible foaming – –
p
Clarifier effluent from existing ETP.
†
Zero concentration.
‡
Below detectable limits.
§
Total dissolved solids.
All values are in mg/l except pH.
 2571 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

3.50 BOD5: ,10 mg/l, and ammonium: , 10 mg/l, can be

3.00 1 recycled/reused within the industry.

1. Inlet to stage I (at 10× dilution)
2. Effluent from stage I unit
3. Effluent from stage II unit
2
Absorbance

2.00
Optimized treatment scheme

Based on the extensive field investigations, and treata-

1.00 bility studies, a modified treatment scheme was pro-
posed for LTC effluent. The schematic of the proposed
3
scheme is presented in Figure 7. Air stripping as pre-
0.00
200.00 300.00 400.00 500.00 600.00 700.00 treatment for removal of ammonia from the process
nm
effluent prior to ETP was already present in the existing
Figure 6 | UV-visible spectra of effluents.
scheme of ETP.
As per the proposed scheme, the stripping of process
The effluent generated after the stage II bio-oxidation effluent should render an effluent of the following quality:
is well within the discharge norms for the parameters pH, pH 8.3– 8.5, COD 15,000 –25,000 mg/l, ammonia 700 –
COD, BOD, ammonia, nitrate, phenol and cyanide. The 1,000 mg/l, and phenol 1,500 –2,000 mg/l. After pre-treat-
UV-visible spectra of equalized effluent, effluent from stage ment, the stripped process effluent along with the combined
I unit and treated effluent from stage II unit indicates effluent stream from the plant area comprising mainly
effectiveness of two stage biological oxidation process in sewage would be routed to the equalization basin for
removing organic pollutants (Figure 6). equalization of flow and characteristics.
The equalized stream will be biologically treated in a
two stage biooxidation process. The stage I biooxidation
unit would operate for oxidation of COD, phenol and
Post-biological treatment
cyanide, while the stage II unit would operate for oxidation
The concentrations of all the major parameters in the of ammonia, residual COD and cyanide. The mixed liquor
treated effluent from stage II bio-oxidation were below the suspended solids (MLSS) should be maintained around
Prescribed Standards for discharge of treated effluent onto 3,000 –3,500 mg/l and 1,500 – 2,000 mg/l in biooxidation
inland surface water (Table 3). Post-biological treatment of units I and II, respectively. The clarified effluent from unit I
the treated effluent was carried out to make it suitable for would be routed to a collection tank where addition of
recycle/reuse. The effect of alum as a coagulating agent in sodium bicarbonate and phosphoric acid would be made for
presence of lime for biooxidation stage II effluent was maintaining the alkalinity to ammonia ratio between 5 – 7
studied. Lime was added to maintain alkaline pH for and the pH at 6.8 –7.2, respectively.
effective action of alum. A COD reduction of 50% was The clarified effluent from the stage II bio-oxidation
achieved at an alum dose of 250 mg/l along with 500 mg/l process would be routed to chemical oxidation unit using
of lime. The treatment resulted in chemical sludge hypochlorite for tertiary treatment. The final treated
generation of 675 mg/l (as dry weight) and there was no effluent would be collected in a collection tank. The
significant reduction in colour. Because of high dose of anticipated characteristics of influent and effluent at
alum required, chemical sludge generation and no effect on various stages of the treatment are presented in Figure 7.
colour removal, use of alum and lime was considered to be The final treated effluent can be reused within the industry.
uneconomic. In the studies with (4%) hypochlorite, 0.5% Dewatering of digested sludge from clarifier-I & II
(v/v) dosage resulted in 40% reduction in residual COD would be carried out in sludge drying beds. After drying,
and significant reduction in colour. The visibly colourless the sludge is to be removed and disposed via secured
treated effluent, with pH: 6.6– 6.8 COD: 73 –121 mg/l, land filling.
 2572
R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry
Desired conditions Desired conditions
Desired conditions in stage I unit Desired conditions in
in stage II unit
in ammonia stripper pH = 7.0–7.8 chlorination unit
pH = 6.8–7.3
pH >10.5 Temp (°C) = 27–37 pH = 6.0–6.5
Temp (°C) = 27–37
Temp (°C) > 45 HRT (d) =3 Temp (°C) = 27–37
HRT (d) =3
MLSS (mg/l) = 2,500–3,500 NaOCl (%) = 0.25 (option 1)
MLSS (mg/l) = 1,500–3,000
CNP ≥100: 5: 1 0.5 (option 2)
Alkalinity/NH3 = 5–7
CNP ≥[Link]

Caustic Bicarbonate and

Phosphate Hypochlorite
addition phosphoric acid
addition addition Reuse
addition
option 1
coal
quenching

Reuse
option 2
gardening
Ammonia Equalization Stage I bio- Stage II bio- Chlorination unit
stripper basin oxidation unit oxidation unit

Raw effluent Stripped raw effluent Equalized effluent Stage I effluent Stage II effluent Treated effluent
pH > 9.0 8.5–8.3 7.5–8.0 6.8–7.5 6.0–6.5 7.0–7.5
Phenol (mg/l) = 3,500–4,000 ≤ 2,000 ≤ 750 ≤ 10 ≤5 ≤2
COD (mg/l) = 25,000–35,000 ≤ 25,000 ≤ 5,000 ≤ 500 ≤ 250 ≤ 150
NH3 (mg N/l) = 2,700–4,000 ≤ 1,000 ≤ 600 ≤ 300 ≤ 20 ≤ 10

Water Science & Technology—WST | 61.10 | 2010

Colour (Hazen) = 30,000 ≤ 25,000 ≤ 3,250 ≤ 2,000 ≤ 500 ≤ 50 (option 1)
BDL (option 2)

Existing New

Figure 7 | Proposed scheme of treatment for low-temperature carbonization effluent.

 2573 R. Biswas et al. | Treatment of wastewater from a low-temperature carbonization industry Water Science & Technology—WST | 61.10 | 2010

Ghose, M. K. 2002 Complete physicochemical treatment for coke

CONCLUSIONS plant effluents. Water Res. 36(5), 1127 – 1134.
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prescribed discharge standards. The laboratory and pilot transformations during aerobic/anoxic sludge digestion.
Bioresour. Technol. 85(2), 147 –154.
plant treatability studies indicated that the process effluent
Kwon, H. K., Woo, S. H. & Park, J. M. 2002 Thiocyanate
from the LTC plant could be biologically treated for degradation by Acremonium strictum and inhibition
removal of ammonia, organic carbon, cyanide using a two by secondary toxicants. Biotechnol. Lett. 24,
stage biological oxidation process. The results from the 1347 –1355.
Li, W. & Zheng, S. K. 2004 A combination of anaerobic and
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aerobic treatment for ammonia laden coke plant effluent: the
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