Indian Journal of Chemical Technology

Vol. 9, January 2002, pp. 54-59

Physico-chemical treatment of coke plant effluents

for control of water pollution in India
M K Ghose*
Centre of Mining Environment, Indi an School of Mines, Dhanbad 826 004. India

Received 3 ! "July 2000:revised 19 Jun e 2001; accepted 26 September 2001

Coal carbonizing industri es in India are important and are growing every year. Naturally found coal is converted to coke
which is suitable for metallurgica l industri es. Large quantities of liquid effluents produced in thi s industry contain a large
amount of suspended solids. high biochemical oxygen demand (BOD), chemical oxygen demand (COD), phenols, ammonia
and other toxi c substances, which are causing serious surface water pollution in the area. There is a large number of coke
plants in the vicinity of Jharia Coal Field (JCF). Working principle of coke plant and the effluents produced has been
described in this paper. One large coke plant was chosen to evaluate characteristics of the effluent and to suggest a proper
treatment method. Present effluent treatment system was no t found to be adequate and a large quantity of a very good
qua lity coke breeze is being lost, which is also causing siltation on the riverbed in addition to surface water pollution.
Physico-chemical treatment has bee n considered as a suitable option for the treatment of coke plant effluents. A scheme has
been proposed for the treatment, which can be suitably adopted for th e recyc ling, reuse or sa fe di sposal of the treated
effluent. Various unit process and unit operation s have been di sc ussed. The process may be useful o n industrial scale for
various si tes so as to maintain a clean e nviro nment.

The importance of coal carbonizing industries in India

1
is very high and growing at a rapid pace It is
producing gas on the one hand and coke (for
metallurgical purposes) and other by-products on the
other. This industry is responsible for entire supplies
of benzene, toluene, anthracene and naphthalene and
coal tar products, which constitute the basic raw
materials for the manufacture of synthetic dyes, drugs
2
and high explosives . In coke ovens, naturall y found
coal is converted into coke, which is suitable for use
in metallurgical industries specially in iron and steel
for blast furnace, in foundry and for domestic
purpose 3 . Large quantities of water are used for the
quenching of hot coke and also for washing gas
produced from ovens. Liquid effluents thus generated
during the process operations are highly polluted and
difficult to handle. Effluents generated from
quenching of coke mainly contain suspended matter
of coke breeze. Water used for washing gas comes out
as strong ammonical liqueur, which con tains hi gh
concentrations of ammonia, phenol, cyanide and other
toxic substances. These effluents are finally
di scharged into the ri ver stream and cause serious
surface water pollution.
*For correspondence: (E-mai l: Ghosemrinal @hotmai l.com )

Wastewater is a misplaced resource and can be

reused advantageously through proper management.
A differentiation can be made between water reuse
and recycling. Reuse impli es utilization of water that
has been previously used for another purpose, and
recycling implies reuse of water more than once for
4
that same purpose . The approaches in wastewater
management should essentially entail waste volume
reduction, waste strength reduction and by-product
recover/. For the abatement of surface water
pollution a fact-finding survey is essent ial. There are a
number of coke plants in operation in the vicinity of
Jharia Coal Field (JCF). In some old coke plants
sufficient area pis not available for biological
treatment. Land disposal for treatment of effluents is
cheap and does not require an expensive wastewater
treatment plant 6 . But the lands available in the
su rrounding areas mostly belong to private owners. If
the effluent is toxic it should not be used for
inigation. So there may be some limitations to
dispose the coke plant effluents for irrigation purposes
to the lands of private owners. For these reasons
physico-chemical treatment may be considered as a
suitable option for the treatment of coke plant
effluents for control of water pollution. One large
coke plant was chosen to evaluate the characteristics

GHOSE: PHYS ICO-CHEMICAL TREATMENT OF COKE PLANT EFFLUENTS

.----~

55

BY PRODUCT RECOVfRY
TAR AMMONIA NAPTHALE~E .
t LIGHT OIL I BTX l

EXHAUSTER
BLENDING &
STORAGE

COKE OVEN GAS FOR

PROCESS USE
RECYCLE
FLUSH I NG LIQUOR

COAL FROM
SOURCES

PRIMARY
COOLER

COAL
PREHEAT

HEAT
EXCHANGER

TAR STOMAGE

COt<E FOR
8UST FURNACES
t. FOUND I5

TAR FOR
PLAtH FUEL
TAR REFINERY

SLUDGE

Fig. I-Coke oven plant wi th by-product recovery

of the effl uent, its quantity and to suggest proper

treatment method to reduce waste strength for
recycling or to dispose it safely to surface water
7
without causi ng pollution problem

Wurking Principle of Coke Plant

Coal is transformed by carbonization into a hard,
porous mass, devoid of volati le matter called coke,
Coking process essenti all y consists of heating of coal
(pyrolys is) in the absence of air o r with limited
oxidant, it decomposes to coke liquid products and
gases. Coking coals are di stingui shed by the fact that
they begin to soften 8 at about 300C. As the
temperature rises, the fluidity of the mass reaches a
maximum and finally the mass solidifies to form
coke. The gases and vapours evolved du ri ng the
plastic stage swells the mass, causi ng the coke to have
a hard porons structure 9 . Non-coking coal does not
soften during heating and products known as char,
crumbles easi ly. The production of the coke consists
of heating bituminous coal in absence of air to final

temperatures of 900- 1100C in an oven or a retort,

drivi ng volati le products that are recovered as tar,
10
light oil and gas .
Several grades of coals are blended, crushed to
about 50 mesh and transferred to a storage bin for
chargi ng " . Th e coking operation is carried out in a
battery of 10-100 individual ovens designed to
provide relatively un iform production of fini shed
products and to recover heat in a way that minimi zes
the fue l requirements. During the coking period, the
coke oven gas is collected through ascension pipe at
the top of the oven, scrubbed in the gas collecting
mai n with weak ammoni a liquor to remove tar, and
di scharged to the byproduct recovery operation . At
the completion of coking, the oven is isolated from
the gas mai 1 and the incandescent coke is pushed into
12
rail cars fot prompt transfer to a quenching tower .
Here, quench water showers the coke to cool it and
prevent furth er loss by combustion, A typical flow
d iagram for a coke plant with byproduct recoveries is
show n in Fig. I .

INDIAN J. CHEM. TECHNOL., JANUARY 2002

56

Effluents from Coke Plant

Methods

The wastewater produced during the carbonization

and classification of fuel is of three basic types' 3 :

Effluent samples from the coke plant were

14
collected each week of Monday and Friday. Since
phenols were present in the wastewater, the samples
were preserved and stored unless they were analysed
within 4 h after collection. It was acidified with
H 3 P0 4 to a pH of 4. One gram of CuSOJI was added
to inhibit biodegradation of phenol. The samples were
kept at 4C. Samples were preserved for COD by 2
mill of H2S04 and for BOD samples were refrigerated
at 4C. The samples were analysed as per "Standard
Methods for the Examination of Water and
Wastewater" 15 . Characteristics of the effluent from
coke plant are given Table 1.

(a) Water used for quenching the coke discharged

from the retorts or ovens
(b) Waste formed during cooling and washing the
gas
(c) Waste formed during the purification of byproducts
Large amounts of water are used when the gas is
washed but as it is only slightly contaminated it may
be recyc led . The most heavily polluted liquors from
the coke plants are the washes from the ammonia
stills, where the condensate from the gas coolers
accumulates. It contains ammonia, phenol, cyanide,
sulphide that are toxic to aquatic life. The insoluble
pollutants, especially tar, form a surface layer that
hinders the access of oxygen from air. Large particles
of suspended matter settle on the bed of the stream
and cause further pollution. Fine suspended particles
clog the respiratory organs of fish, making it
impossible for them to live in such a stream. If there
is insufficient dilution, thiocyanides, free lime and
pyridine may also cause serious difficulties. Much of
the dissolved oxygen is consumed by sulphur
compounds, mainly sulphides which also have direct
harmfu l effects on fish life depending on temperature,
pH and dissolved oxygen . Unless removed from the
effluent, oil and grease lead to the formation of oil
slicks, which limit the diffusion of oxygen from air
into water.

Details of the Study Area

The coke plant studied, is situated at a distance of
10 km from Dhanbad, 1155 km from Delhi and 269
km from Calcutta at latitude from 23 38' to 23 40' N
and longitude from 806 22' to 86 30' E. It was built
in 1915 and is well connected by rails and roads. It
takes water from a river Ekra Jore Nallah and
discharges its effluent to the same river. This river
later joins the river Damodar. Information on the coke
plant effluent is given below.
I.
2.

3.
4.
5.
6.
7.
8.

Coking temperature
Coking hours
No of batteries
Total number o f ovens
Quantity of coal charged
Yield of coke
Water consumed for industri al
purpose
Waste water generation

1050- 1 100 c
26-28 h
2 nos. in 1915
40 ove ns per battery
9 t pe r oven
7 t per oven
700 kl I day
175 -200 kl/day.

Results
The pH of the effluent was found to be slightly
alkaline in nature. The dissolved oxygen (DO) was
found to range from 1.42 to 3.17 with an average of
2.39 mg/1. COD value of the effluent was also found
to exceed the permissible limit of 250 mg/1 as per IS
2490 due to the presence of suspend solids of coal
fines and organic matter. High value of BOD showed
the presence of biodegradable substances. The aerobic
decomposition of organic matter takes dissolved
oxygen from the river water and is responsible for
depletion of DO. Average oil and grease content of
the effluent was found to be 19.61 mg/1. Increase of
dissolved solid content observed in comparison to the
raw water indicates contamination of inorganic salts.
Suspended solids in the effluent were found to be very
high ranging from 1521 mg/1 to 2031 mg/1 as
compared to the tolerance limi t of I 00 mg/1.
Ammonical nitrogen was contaminated during the
extraction of coal tar from the coke oven gas
ammonical nitrogen . Contamination with nitrate
nitrogen, phenolic compounds, cyanides and hardness
was also observed.

Discussion
Coke plant effluent contains a large amount of
suspended solids. After quenching of coke a large
quantity of effluent is generated, which mainly
contains suspended coke breeze. Settling tanks have
been provided for the settlement of s uspended solid,
but it was observed that the numbers were not
adequate and sufficient retention time for the
separation of total suspended solid (TSS) was not
maintained. So a large amount of coke breeze is being
lost every day along with the effluent. This showed
the ineffectiveness of the present effl uent treatment

GHOSE: PHYS ICO-C HEM ICAL TREATMENT OF CO KE PLANT EFFLUENTS

57

Table !--Characteri stics of coke plant effl uents from the coke plant (average results)
Parameters

pH
Temperature (C)
Dissolved oxyge n
COD
BOD
Oil and grease
Dissolved solids
Ammonical nitrogen
Nitrate nitrogen
Total hardness
Ca-hardness
Mg-hardness
Phenols
Cyanide

Min .

Max .

Avg.

Tolerance.
limit, IS: 10,500,
Drinking water
standard

Tolerance
limit IS : 2490
Effl uent water
standard

7. 1
28 .7
1.42
525.39
63.90
16.92
945.00
336.93
43.2 1
440.21
72.00
352.00
81.20
8.2

8.5
32.0
3. 17
810.30
92.30
24.23
1287.82
562.30
55 .39
495.39
96.00
406.07
123.60
20.7

8.28
30.40
2.39
692.11 ---

5.5-8 .5

5.5-9.0
40C

80.60
19.61
1122.65
454.95
49.30
462.76
88.35
37 1.91
92.82
10.3

. 01
500

250
30
10
2 100
50

45
300

. 001
. 05

I
0.2

Note: All parameters except pH are ex pressed in mg/1 un less otherwi se noted

system. At the discharge po int, the river water has

taken a black coloured look due to the deposition of
coke breezes. So, in addition to the surface water
pollution and siltation on the riverbed a huge quantity
16
of costly coke breeze is being lost every day High
BOD, COD, phenol content of effluent are causing
seriou s surface water pollution. The test result reveals
that proper treatment of the effluent is needed before
di scharging to surface water bodies.

Physico-Chemical Treatment of Coke Plant Effluents

Means of treatment in which the application of
physical forces predominate are known as unit
operatio ns. Mea ns of treatment in which removal of
contamin ants is brou ght by the addi tion of chemicals
or by biological actiVIty are known as unit
17
processes Th e unit operation s and chemical unit
processes occur in various combinations in different
treatment systems, but th e fundamental principles of
18
their operation do not change . The principles
developed can be applied to des ign the coke plant
effluent treatment 19 The proposed scheme for the
phys ico-chemi cal treatment o f coke-plant effluent is
given in Fig. 2 and unit operati o ns and unit processes
in vo lved have been di sc ussed.
Unit Operation
Mixing is an important operation where one
substance must be comp lete ly intermixed with

another. Lime is to be mixed in the secondary settling

tanks . Chemical s are also mixed with sludge to
improve the de-watering characteristic before vacuum
filtration. Flocculation is to be promoted by gentle
stirring with slow moving paddles. The action is to be
aided by the installation of stationary stator blades,
located between the moving blades, that serves to
breakup the mass rotation of the liquid and promote
mixing. Increased particle contact will promote floc
growth. Agitation should be carefully controlled so
that the floe particles will be of suitable size and will
settle readil y.
Sedimentation of suspended particles that are
heav ier than water is to be carried out by gravitational
settling. This operation is to be used for chemical floc
removal and for solid concentration in sludge
thickeners . The primary purpose is to produce a
clarified effl uent, but it is also necessary to produce
sludge with so lid concentration that can be easily
handled and treated . [n the design of sedimentation
basins, du e co nsideration should be given to produce
both a clarified effl uent and a concen trated sludge.
Multimedia filtration is to be used to reduce fin e
suspended partic les from the wastewater before its
passing the activated carbon adsorption, Mechanical
and di sso lved air flotation thi ckeners are to be used to
thicken sludge. Solid concentration of 5 - 6 % or
more can be obtained from mi xtures of sludge.
Volume reduction is very desirable. Important

INDIAN J. CHEM . TECHNOL., JANUARY 2002

58

EFFLUENT FROM PROCESS

FOR TREATMENT

a:

lr~

a:
....

:!z

....a:

Q.

0:
,_.

RECARBONATION
TANK

oo
....
l:~
a:
-,_.
>-_,
_._
:::>u..
:I:

Vl

"'
z

<{

!:::;

,_Vl

"-Z

:::> Vl
u.D

0
z-

o>.,a.
a:O:

<(0
._,Vl
D

e<
1-0:

_....

~0

:I:

zO
u...a.

_.-

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.... 0

8u...
t-Vl

.........
a: a:
<{::>

1-

1-

<{

UHf SlU06f

SlOW DOWN

Fig. 2-Proposed sche me for complete treatment of coke plant effluent

considerations in designing a thickener are to provide

adequate time to meet peak demands and to prevent
septicity with its attendant odour problems during the
thickening process.

Ammonia Stripping
Stripping with steam or hot gas such as air can
remove most of the ammonia, carbon dioxide and
hydrogen sulfide20 . Other materials such as phenols,
cyanide and light organics can also be removed.
Ammonia stripping towers can be very effective in
ammonia removal. The basic equipment for an
ammonia striping system includes chemical feed,
stripping tower, pump and liquid spray system, forced
air craft, and carbonization system. Important design
parameters for the system are average and peak
design flow, surface loading rate, chemical dosage,
tower height and air-to- water ratio.

Ion exchange for Ammonia Removal

Wastewater is to be passed through a bed of
clinoptilolite (a zeolite resin) which selectively
removes the ammonium ion 21 When the resin
becomes saturated, it is regenerated with a lime slurry
containing sodium chloride. The lime solution after
regeneration of the resin must be processed to remove
the ammonium ions that the solution can be reused to
remove the ammonium ions, so that the solution can

be reused. Air stripping of ammonia is a feasible

method. The stripped ammonia gas is passed through
an absorbed material, which has high selectivity for
ammonia. Proper disposal of ammonia bearing
absorber material is necessary . Major equipment
includes an ion exchange bed, bed regeneration
system, ammonia stripping tower and ammonia
absorber material. The design parameters are average
and peak design flow, ion-exchange capacity of the
resin bed, concentration of ammonia, percolation rate
etc 6 . Singh and Prassad 22 reported that the 13x
molecular sieve showed more than double the
adsorption capacity for ammonia compared to SA
zeolite.

Carbon Adsorption
Carbon adsorption is to be used to remove soluble
refractory organics. The process consists of
entrapping organic material on the carbon surface.
The most common method is the use of granulated
carbon columns. The treated wastewater is percolated
through the column until the column becomes
saturated with organic material. It is then removed
from service and burning off the organic materials in
a special furnace regenerates the activation. About 5%
loss of carbon can be expected with each cycle.
Activated carbon can effectively remove bacteria and
viruses. It also removes organometallic compounds,

GHOS E: PHYSICO-CHEMICAL TREATMENT OF COKE PLANT EFFLUENTS

pesticides, chlorinated compounds, chlorine and many

other compounds that are not removed in the
conventional biological secondary process. Major
equipment commonly needed for the system are
carbon column, granul ar activated carbon, feed and
back wash pump and piping, and carbon regeneration
system. Common design parameters include average
and des ign flow, influent characteristics, effluent
quality, contact time and adsorption capacity of
carbon.

Conclusion
Coke plant effluents containing a large amount of
suspended solids, high BOD, COD, phenols,
ammonia and other toxic substances, are causing
serious surface water pollution problem in the area.
Physico-chemical treatment can be considered as a
suitable option for the treatment of coke plant
effluent. By adopting the suggested treatment scheme
it may be feasible to design an effective treatment
plant for coke plant effluent. and the treaied effluent
can be used for recycling or safely discharged to
water bodies.The methodology adopted may have
formed a guideline for the treatment of coke plant
effluent and can be useful on industrial scale at
various sites and a clean environment can be
maintained.
Acknowledgements
The author is thankful to Ministry of Environment
and Forests, Govt. of India, for supporting grants for
infrastructral facilities at Centre of Mining
Environment, Indian School of Mines, Dhanbad.
Assistance from Sri S . Roy, Bihar State Pollution
Control Board and from Dr. P. K. Sen, MECON Ltd.
for the work is also acknowledged.

59

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8
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16
17
18

19
20
21
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