Whereas the Parliament of India has set out to provide a practical regime of right to
information for citizens to secure access to information under the control of public authorities,
in order to promote transparency and accountability in the working of every public authority,
and whereas the attached publication of the Bureau of Indian Standards is of particular interest
to the public, particularly disadvantaged communities and those engaged in the pursuit of
education and knowledge, the attached public safety standard is made available to promote the
timely dissemination of this information in an accurate manner to the public.
1 +, 1 +
01 ' 5
Jawaharlal Nehru
! $ ' +-
Satyanarayan Gangaram Pitroda
! > 0 B
BharthariNtiatakam
IS : 9841 - 1981
( (Reaffirmed
2005) )
Reaffirmed 1995
Indian Standard
GUIDE FOR TREATMENT AND DISPOSAL OF
EFFLUENTS OF FERTILIZER INDUSTRY
( Secmd Reprint FEBRUARY
UDC
628.543
(026) ; 63 l-8
CopVrrghr 1981
BUREAU
OF
JNDIAN
MANAK BHAVAN,
9 BAHADUR
NEW
199X )
BElx1
STANDARDS
SHAH
ZAPAR
MARG
llooo2
November
1981
IS : 9841- 1981
Indian Standard
GUIDE FOR TREATMENT AND DISPOSAL OF
EFFLUENTS OF FERTILIZER INDUSTRY
Water Sectional
Committee,
CDC 26
Representing
Chr/irtmn
Geo
DR T. R. BHASKARAN
Members
SHRI S. BHiIOTHALINGAhl
SHRI J. D. JOYSINCH ( Alternate
CHIEF WATEK ANALYST, KINCI
1SW WTE, MADRAS
SHKI L. M. CHOUDHRY
Director
of Public
Health,
Government
Nadu, Madras
Haryana
State Board for the Prevention
of Water Pollution,
Chandigarh
of Tamil
& Control
Indian
Chemical
Calcutta
Manufacturers
Association,
National
Test House, Calcutta
The Fertilizer
( Planning
& Development
Ltd, Sindri
Uttar
Pradesh
Water
Polhtion
Control
Board, Lucknow
) India
Prevention
and
& Control
( CSIR
CSIR ),
1,
New
Karnataka
Electricity
Authority,
New Delhi
( Continued on page 2 )
@ Copyrlghr 1981
BUREAU OF INDIAN STANDARDS
This publication is protected under tho I&an Copyrlghf Acr ( XIV of 1957 ) and
reproduction in wholo or in part by any mean8 except with written pormirrlon of the
publbbor ahall bo doemod to be 81) infrigement of copyright under the raid Act.
IS : 9841- 1981
( Continued
from puge 1 )
Represetrring
Members
Delhi
Water
Supply
&
taking, New Delhi
Sewage
Disposal
Under-
SHRI H. S. PrRI
SHRI QIMAT RAI ( Alternate
SHRI B. B. RAO
Ministry
of
Works
& Housing
DR I. RADHAKRISHNAN ( Afternate
SHRI B. V. ROTKAR
1
Central
Board for the Prevention
Water Pollution. New Delhi
DR K. R. RANGANATHAN ( Alternare )
Engineers India Ltd, New Delhi
SHRI K. RUDRAPPA
SHRI S. N. CHAKRABARTI ( Alternate )
( Continued
and Control
& Control
on page 41
IS : 9841- 1981
Indiun Standard
GUIDE FOR TREATMENT AND DISPOSAL OF
EFFLUENTS
OF FERTILIZER
INDUSTRY
0. FOREWORD
0.1 This Indian Standard was adopted by the Indian Standards
on S June 1981, after the draft finalized by the Water Sectional
had been approved by the Chemical Division Council.
Institution
Committee
for adoption
have been selected
of their adoption by the industry.
IS : 2490 (Part VIII)-1976 Tolerance limits for industrial effluents discharged into inland surface waters : Part VIII Phosphatice fertilizer industry (first revision )
IS : 2490 ( Part IX)-1977
Tolerance limits for industrial effluents discharged into inland surface waters : Part IX Nitrogenous
fertilizer industry (fjrst revision)
IS : 3306-1974 Tolerance limits for industrial effluents discharged into
public sewers ( first revision )
IS : 3307-1977 Tolerance limits for industrial effluents discharged on
land for irrigation purposes (first revision )
IS : 7968-1976 Tolerance limits for industrial effluents discharged into
marine coastal areas.
0.8 Methods of sampling and test for industrial effluents are covered in
various parts of IS : 24881.
1. SCOPE
1.1 This standard
covers methods
of treatment
and disposal of effluents
from nitrogenous
and phosphatic
fertilizer industry.
It includes available
data and information
on the sources, characteristics,
volumes,
pollutional
effects of the effluents, ways of waste prevention
and methods of their treatment and disposal.
*Criteria for controlling pollution of marine coastal areas.
TTolerance limits for inland surface waters subject to pollution (first revision).
$Methods of sampling and test for industrial effluents :
Part IV - 1974
Part I - 1966
Part V - 1976
Part II - 1968
Part III - 1968
1s : 9841 - 1981
2. DESCRIPTION
OF PHOCE:SSES
INVOLVEI)
Fertilizer
Industry
IS:9841-
1981
sulphate
is produced
IS:0841
- 1981
2.1.3.3 Ammonium
sulphatc
is ;~.lso manufactured
from natural
or
byproduct gypsum.
The ground gypsum is reacted with ammonium
carbonatc producing
ammonium
sulphatc and chalk.
The chalk is separated by
filtration and the liquor is evaporated
and crystallized.
The ammonium
sulphatc crystals arc scparatcd by filtration and dried.
2.1.4 Anunoniur~z hritrutc, and Cdcimz Arnnwniuw Nirratc Production
Ammonia
reacts with nitric acid in a neutralizer
producing
ammonium
Ammonia
and nitric acid are prohcatcd
with the vapours of the
nitrate.
ncutrali7cr.
In the neutralizer,
concentrated
ammonium
nitrate solution
is
Ill
producctl
which is furthcr concentrated
in vacuum
concentrators.
ammonium
nitrate production,
the concentration
is carried out up to molten
nitrate which is then sprayed from a prllling tower against an upward stream
In
the case of calcium
of air to produce
prilled
ammonium
nitrate.
;tmmonium
nitrate (CAN), the concentrated
liquor is pumped and sprayed
Into the granulator
which is also fed with a measured quantity
of limestone
powder and recycle fines.
The hot granules arc dried, scrcencd, cooled and
coated with soapstone dust in a coating drum and stored.
2.1.5 Nttric Acid and .Su/p/mu~~
Ac,iti Pwductior~
In the industries where
ammonium
nitrate and anlmonium
sulphatc are produced,
nitric acid and
bulphuric acid production
plants arc alho installed.
Sulphuric
acid and
nitric acid are also required for the production
of phosphatic
fertilirers.
Nitric acid is produced by oxidation of ammonia over a noble metal catalyst
and absorbing
III
water.
Sulphuric
acid is normally produced by burning
sulphur to form sulphur dioxide which is then oxidized to sulphur trioxide
over vanadium
catalyst:
sulphur trioxide is then absorbed in concentrated
sulphuric acid.
2.1.6 Armnonito~l C/dot-i& Production ~-- Ammonium
chloride is normally
obtained as a byproduct in the production
of soda ash.
Sodium chloride is
reacted with ammonium
bicarbonate
producing
ammonium
chloride and
sodium bicarbonate.
The ammonium
chloride solution is filtered, evaporated
and crystallized.
Ammonium
chloride
is also manufactured
by direct
neutralization
of ammonia with hydrochloric
acid gas.
2.2 Phosphatic Fertilizer Industry
2.2.1 Pkosplwric Acid--- In the manufacture
of phosphatic
fertilizers, ihe
production
of phosphoric acid is the basic building
block.
The first step
involved
in phosphoric
acid production
is grinding
of rock phosphate.
Ground phosphate rock is mixed with sulphuric acid after the acid has first
been diluted with water to 55 to 70 percent sulphuric acid concentration.
The acidulatcd
rock is digested and retained for several hours in attack
vessels.
The rock phosphate is converted into gypsum and phosphoric acid.
Some of the fluorine contained in the rock phosphate
is evolved from the
attack vessels as silicon tetrafluoride
and hydrofluoric
acid.
Both silicon
IS : 9x41 - 19x1
VOLUMES
3.1 Nitrogenous
Fertilizer
AND CHARACTERISTICS
Industry
(Sources
OF EFFLIENTS
of Effluents )
3.1.1 Ammonia
Plant
3.1.1.1
From raw material handling, storage and preparatron
sections.
normally a small stream of effluent containing
mainly some coal dust, fuel
oil or naphtha is discharged, depending on the feed stock used
8
IS : 9841 - 1981
3.1.1.2 Where coal is used as feedstock, a considerable qllantit), of
quenched ash is discharged continuously from the coal gasification sectron.
The ash slurry from the direct scrubber recirculating water settling system
containing some cyanides is also discharged to the ash pond.
3.1.1.3 When naphtha is used as feed stock. the chlucnts from the oil
gasification section and carbon recycle section contain high concentration of
oil, in addition to the carbon particles and sulphidc impurities. Catal! tic
steam reformation process is mostly adopted when naphtha i4 USC{!nc
feedstock. No liquid effluents are produced in this process.
3.1.1.4 In the partial oxidation process. finely divided carbon is proJucc~~
Some built-in facility in the plant exists for recycle and reuse of this wrhor
in the process itself, but due to unforeseen accidental failure of the $!stcr;.
some carbon slurry may be discharged for a short period. This carhcm
slurry may also contain some cyanides and sulphides.
3.1.1.5 Depending on the absorbent used for the purification of raw ga>.
some toxic chemicals, namely, arsenic, MEA, vanadium, methanol and some
alkali are discharged in a small stream.
3.1.1.6 From the CO-conversion unit, some quantity of condensate
containing ammonia and catalyst dust is discharged.
3.1.1.7 During the commissioning of the plant and initial start-up some
quantity of ammonia is discharged when the catalyst reduction operation is
carried out. Normally, this effluent emanates once every 2 to 3 years.
3.1.1.8 From the ammonia
containing oil is discharged.
discharged
water is
dioxide compression
chcml-
ammonium
nitrate
is discharged
3.1.3.3 Occasional
spillage and leakage from process
an cfflucnt containing
ammomum
nitrate.
3.1.3.4 The cooling water blowdown
containing
chemicals and biocides is discharged continuously.
3.1.4 Amnioitium
Sulphtc
may give
some
con-
rise to
conditioning
Plant
done,
containing
quantity
of
and crystallization
section,
sulphate is discharged.
a small
effluent
conditioning
stream
eflluent
chemicals
and
3.1.5 Amtnotliutn Cltloridcj Plant -- The efBuents are mixed up with soda
and contain
ammonia
and ammonium
chloride.
effluent
ash plant
However, this efllucnt is discharged in a limited quantity.
3.1.5.1 In the direct process, the main effluent is the wash water used to
This will be of considerable
volume
wash the gases before they arc let out.
aud will contain ammonia.
10
IS : 9841 - 1981
3.2 Phosphatic
3.2.1 Phosphoric
Acid Plant
3.2.1.1
During
the digestion
of rock phosphate
with acid, silica,
fluorine and other impurities
present in it are evolved as silicon fluoride,
hydrotluoric
acid, dust, etc. These off-gases are scrubbed
with water.
A part of the scrubber liquor is discharged continuously.
gypsum
which
filtration
contains
quantity
of
phosphorus
Supcrphosphute
- In the manufacture
of triple superphosphate
phosphate bearing off-gases from the reaction vessels, granulaare scrubbed with water.
A part of this scrubber liquor finds
the effluent stream.
3.2.4 Ammonium
Phosphates
--- The main effluent normally discharged
from ammonium
phosphate plant contains
ammonia, phosphate, fluorine,
dust, etc.
The contaminants
indicated
above
are evolved during
the
and granulation,
drying
and sizing operations.
neutralization
reaction,
These off-gases are scrubbed with phosphoric
acid and the entire scrubber
liquor is put into the reactor.
3.2.5 Nitrophosphates - In nitrophosphate
production also, dust, fluorine,
phosphate, ammonia, ctc, containing
off-gases from digestion and ammoniation section and also from drying, granulation
and sizing sections are scrubbed with water for reduction
of the pollutants
in the emissions of nitrophosphate
plant.
A portion of the scrubber liquor is discharged as effluent
continously.
3.2.6 During the processes of manufacture
of phosphoric
acid and
phosphatic fertilizers
considerable
quantity
of recirculating
cooling water is
blowdown
containing
used.
A continuous
stream of cooling
water
conditioning
chemicals and biocides is discharged from the cooling towers
IS:98413.2.7
1981
Sulphuric Acid Plants -
gets contaminated
3.2.8 Nitric Acid Plant -- When there are leakages, the cooling water gets
contaminated with nitric acid.
3.3 Quantity of Effluent -- The total quantity of finally treated effluent
discharged from fertilizer industries varies widely, depending on the raw
material used, the end product obtained and the process adopted for
A 1 000 tonnes per day urea plant having
the production of fertilizers.
recirculating cooling water system and all the auxiliary facilities required for
production, generally discharges 8 000 to 12 000 m3/day effluents, while a
phosphatic
fertilizer plant with recirculating cooling water system and
auxiliary facilities and having a production capacity of about 100 tonnes of
P?O, per day as fertilizer generally discharges 3 000 to 6 000 m3/day effluents.
3.4 Characteristics
of Effluents
3.4.1 The main pollutants from the nitrogenous and phosphatic fertilizer
industry along with the auxiliary facilities are indicated below:
a>Ammonia
phosphates,
biocides, etc;
concentra
*Data based on Revised Draft Report on Fertilizer Industry Pollution and Contrc
Measures submitted to the Central Board for Prevention and Control of Water Pollutio
by Tata Consulting Engineers, Bombay.
12
IS :9841- 1981
3.4.2.1
Coohg
tower blowdown
Concentration
Contaminant
a) Suspended
b) Dissolved
30-3 000
solids
300-3 200
solids
0.4-40
c) Free ammonia
Ammoniacal
Range ( mgjl )
20-400
nitrogen
e>Phosphates
f) Chromium
IO-30
8) Chlorides
8-18
h) Sulphates
20-50
j) Calcium
SO-240
k) Zinc
Traces
m) Oil
10-I 000
6-R
Boiler blow-down
Contaminant
Concentration
.a) Phosphorus
10
b) Dissolved
solids
100
c) Suspended
solids
10
d) Free ammonia
e) Ammoniacal
e
nitrogen
f) Oil
;0
13
Range
( Ifg/J )
IS : 9841- 1981
3.4.2.4 Ammonia plant
Contaminant
a) Suspended solids
100-I 5000
1 000-3 000
200-I 500
o-2
5000
SO
200
25
7
75
O*l
b)
c)
d)
e)
f)
g)
h)
j)
k)
m)
Dissolved solids
Ammoniacal nitrogen
Arsenic
Carbon dioxide
Chlorides
Sulphates
Calcium
Cyanides
Sodium
Vanadium
Suspended solids
Dissolved solids
Ammoniacal mitrogen
Urea
Sulphates
Chlorides
Calcium
Phosphates
100
1000-3 000
500-2 000
340-20 000
200
80
20
5
concentra.
*Data based on Revised Draft Report on Fertilizer Industry Pollution and Contra
measures submitted to the Central Board for Provontion and Control of Water Pollutic
by Tata Consulting Engincqg,,Bombay.
14
t
;.
IS : 9841- 1981
d)
e)
f)
g)
Traces
52
30
10
Chromates
Chlorides ( as Cl )
Sulphates ( as SO, )
Calcium ( as Ca )
Contaminant
a) Dissolved
( fixed )
b) Sulphates
c) Alkalinity
d) Hydroxide
e) Silica ( as
f) Zinc
solids
9 661
918.3-3 813
2 150-2 950
450-515
0.80
0.10
( as SO* )
( as CO, )
SiO, )
a) Suspended solids
b) Dissolved solids
cl Biochemical oxygen demand
150-6Qo
644-980
35-175
d) Fluorides ( as F )
e)
f)
g)
h)
1 920-2 163
42-234
40-336
32-86
0.4-l
Chlorides ( as Cl )
Sulphates ( as SO,,)
Calcium
Phosphates ( as PO,)
1480
6.7
1
488
IS : 9841 - 1981
200
c) Sulpllates ( as SO,)
f)
Ammoniacal
10
nitrogen
g) Phosphates ( as PO, )
h) Oil and grease
4. METHODS
OF TWLATMENT,
Traces
UTILIZATION
AND DISPOSAL
4
b)
Effluents containing
suspended
solids above 100 mg/l should
combined together as far as practicable;
Oil bearing effluents should be combined as far as possible;
c>Highly
4
4
f)
effluents
should
be separated
g) Eflluents containing
be
of
and
IS : 9841 - 1981
h) Arsenic and cyanide
bearing
j) Efiluents containing
from other effluents:
fluorides
k) Sewage effluents
m) Storm water
effluents.
should
and drain
eflluents
should
and
phosphates
be treated
water
separately
should
be stored separately;
are to be segregated
as far as possible
and
depending
plant
on
of Effluents
4.3.1 Amtnonia
NitrL?+ztr
Various
processes
have been developed
for removalrecovery
of ammonia nitrogen from effluents.
These processes
basically fall in two categories
: ( a ) Physio-chemical.
:.nd ( b ) biological.
17
PROCESS
TREATMENT
WATER
PLANT
SULPHURIC
ACID
PLAN1
HANDLING
SECTION
GENERATION
17
18
19
20
21
II9riJ
Y
r-
15
13
'
I
16
II,
In
uNCON
TED
STREA
0
FK.
TYPICAL
yJy7
;;$T&E
1
NT
TO
RECE!VI:IG
WATER
1.
2.
3.
4.
5.
6.
7.
8.
z
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
5:.
22:
23.
Efluent Streams
Effluent containing suspended carbon, cyanide,
sulphide, etc
Condensate containing oil
Cooling tower blowdown containing CrO,
and PO,
Process condensate containing ammonia
Catalyst reduction NH%
Reactor draining, overflow of tanks and plant
washings
Vacuum condensate containing ammonia and
urea
Cooling tower blowdown containing CrO,
and PO,
Condensate containing oil
Acidic effluent
Alkaline effluent
Acidic effluent
Raw water treatment plant sludge
Boiler blowdown
Ash slurry
Oily effluent
Concentrated fluosilicic acid solution
Effluent containing fluorine and phosphate
Gypsum slurry
Effluent containing fluorine and phosphate
Sewage effluent from toilets and washings
Uncontaminated effluent stream
Final effluent of the factory after treatment
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
Treatment of Efluent
Suspended matter settling
Cyanide, sulphide removal system
Oil separator
Evaporation of ammonia
Collection pit for ammoniacal effluent
Air/steam stripping of ammonia with recovery
of ammonia in case of steam stripping
Thermal urea hydrolysis ammonia recovery
Chromate phosphate removal system
Neutralization
Oil separation
Ash settling pond
Oil separation
Recovery of fluosilicic acid
Fluorine and phosphate removal system
Gypsum settling pond
Sewage treatment
Biological treatment
Mixing pond
IS : 9841 - 19x1
a) Air
stripping -~ The
concentration
of ammoiGa
nitrogen
in
effluent can be reduced considerably
by adopting
air strIpping of
ammonia
from the effluent at an elevated pH
Ammonium
ions
( NH, ) in water exist in equilibrium
with NH, as follows:
NH,+
=: NH,
AMHONl
AIR
WASTE
AMMONIACAL
ALKALI
STREAM
EFFLUENT
CLARIFICATION
I
SLUDGE
IS : 9841-
1981
NH,NO,,
/- HNO,
{
t H,SOI
7
+ RH _- - RNH,
HNO,
H,SO,
>
J
+ RNH,--:-
RH
+- ROH -+
H,O +
f N&NO,
(
1 (NH,), SO4
r RNO,
(
(
+ NH, OH -a
R,SO,,
ROH
.:
R,SO,
[
NH,NO,
{
((NH,),
SO,
IS : 9841 - 1981
ACID
7
AMMONIACAL
DISPO~
FILTRATION
EFFLUENT
t
FIG.
AMMONIACALEFFLUENT
NLlJTRALIZ4TlON
EXCHANGER
;r
4MMONIUM
SALT
SOLUTIOV
I'KEATMENI.
1%~CATION EXCHANL~
sulphuric acid.
The acidic water then passes through the bed of
anion resin in base form where the acidic ions are absorbed.
The
effluent water from the second bed is very low in ammonium
salts.
and can be reused in the process as make up water in boiler feed
water treatment plant and may be used in the boilers after polishing in mixed bed ion cxchangc system.
The cation exchange resin
holding
the ammonium
ion can be regenerated using sulphuric or
nitric acid to form ammonium
sulphate or nitrate solution.
The
anion resin holding the acidic ion is regenerated using a solution
of
ammonium
hydroxide to form more ammonium
sulphate or nitrate
The ammonium
salt solution thus produced may be used
solution.
in the process for the production
of ammonium
sulphate or nitrate,
provided such facilities arc available at site. It may be noted that
soluble inorganic
contaminants
in the waste water will also find
their way into the product.
4.3.1.2
Biolo~icd proccsw Y
IS : 9841 - 1081
nitritymg
organisms
( Fig. 5 ). The mtrates irl turn
rcact~d
I,)
another anaerobic pond in the presence 01 biodegradable
carbon
compound
employing the denitrifying
process Iorm elemental
nitrogen.
The process may be rcprcsented as follows:
Ammonia
nitrogen
Aeration
Nitrifying
organism
Nitrate
nitrogen
Organrc
carbon
---+ N lJ
I)enitrifyin;
organism
(0,
ORGANIC
-(SEWAGE
C+.-1301
- ._~__ .---.
~_.
_--_c
J h!E>I,jL!,L)
NUTRIENT
ALKALi
o----AMt.:ON!ACAl.
EFFLUENT
ORGANIC
CARBON
-___
METHANOL)
r_lli
(SEWAGE/
NlTRATf
BEARING
Cl_Ai?iF~i?.i
EFFLUENT
CIr:
IS : 9841 - 19x1
Oxidation pond-like ponds may be used for the culture of algae
(Fig. 6). Carbon
dioxide may bc supplied by biodegradation
of
organic matter or dilute carbon dioxide may be dil~us~d through a
network of carbon dioxide difTuscrs in the pond.
Other ncccssary
nutrients
for algal cultures may be supplemented
in the pond.
With suitable detention t&c, depth of the pored. conccntmtjon
of
algae, concentration
of ammonia nitrogen,
sunlight. etc. the upt:tkc
of ammonia
nitrogen in the cell formation
of algal cell> is quite
appreciable.
Algae thus produced may be harvested
u>ing a suitable process and utilized as manure.
4.3.2
Nitropv~
-I- 2H,O +
(NH,),CO,
The pH increases
with the progress of hydrolysis;
under properly
maintained conditions,
over 95 percent of urea can be hydrolyzed
in 2-t h.
The hydrolyzed
solution containing
ammoniacan
be treated by any of the
methods described under ammonia removal.
4.3.2.3 Reduetion
of nitrates can be clfected
process (Fig. 5) described under 4.3. 1. 2 (a).
by
the dcnitrilication
IS : 9841- 1981
4.3.4 pH-Sometimes
the effluents are highly acidic or alkaline in nature.
When both acidic and alkaline waste waters are found, they may be mixed
Otherwise for neutralization
of acidic effluent,
suitably for neutralization.
lime or soda ash may be used and for neutralization
of alkaline eflluent
In the process of neutralization
proper mixing
sulphuric acid may be used.
is very important.
This can be effected by flash mixing or mixing by
agitation or recirculation.
4.3.5 Oils ad Greases - Oils and greases normally
discharged
in fertiFurthermore,
a
lizer industry eflluents are mostly in non-emulsified
form.
majority of these insoluble
oils are lighter than water and therefore they
Insoluble oils lighter than water are usually sepawill float on its surface.
rated in settling tanks provided with an adjustable
skimming
weir (Fig. 8).
These settlers are usually termed as gravity type mechanical
oil separators.
The oils readily float on these separators
and the depth of the weir is
adjusted according to the amount
of oil present in the waste water.
The
collected
oil is skimmed by mechanical
means periodically.
A properly
designed oil separator can reduce the oil content
of the effluent
below
50 mg/l. If a greater degree of oil removal is desired, the effluent from the
oil separator may be passed through active carbon or a porous coke bed by
which the oil and grease content of the effluent is reduced to 3 to IO mg/l.
4.3.6 Atwnic -- In fertilizer industry, arsenic is a constituent
ofabsorbent
liquids used for carbon dioxide removal.
Normally adequate arrangements
are provided in the plant so that arsenic does not find its way out in the
eflluedt.
But in actual practice, due to leakages in pump glands, flanges,
joints, etc, and also from spillages, some arsenical solution is discharged.
The quantity of this arsenical solution can be controlled
within reasonable
limits by good housekeeping.
The arsenic solution which is discharged
even after taking all the precautions
is completely
separated
from other
waste waters.
The waste water containing
arsenic is then filtered, concentrated, further filtered through active carbon filter if necessary and recycled
in the process.
When it is not possible to take it into the process, the
arsenical solution is evaporated to dryness and the solids are placed in concrete drums, sealed properly
and buried underground
or disposed of into
the deep sea far away from the coastline.
4.3.7 Cltrotttate atd Phosphare -- Fertilizer
industry
requir-es a high
quantity of cooling water during processing of fertilizers.
In most of the
Suitfertilizer factories. cooling water is recycled through
cooling towers.
able inhibitors for control of scaling/corrosion
properties of circulating water
are dosed into the cooling water system. Various inhibitors are used depending on the local conditions.
Most of the plants use combinations
of chromate,
phosphate and zinc in different proportions.
Normally.
zinc is used in a
very low concentration,
therefore, any specific treatment for the removal
of
zinc is not considered necessary.
In the treatment for removal of chromate
29
IS : 9841 - 1981
AGENT
OIOX.!DE
FERROUS
SULPHII+/
I
LIME
C
ACID
CGOLtNG
BLOWDOWN
AND
TOWER
ACID
NEUTRACIZATIClN
SETTLING
PHOSPHATE
Dspos2
/
1
SLUDGE
FIG. 9 CHROMATE
BEARINGEFFLUENTTREATMBNT
The cooling tower blowdown which contains chromate is collected in a
tank and the%pH of the water is lowered to the range 2 to 4 by adding
sulphuric acid. After mixing with the acid, ferrous sulphate, sodium
sulphite, sodium metabisulphite or sulphur dioxide is added to reduce
hexavalent chromium.
For removal of lg of CrO, about 10 g of ferrous
sulphate, 2.5 g of sodium sulphite or 1.5 g of sulphur dioxide is required.
After reduction, lime is added to the effluent for raising the pH and precipitation of chromium.
The settled effluent is allowed to be discharged
The reactions which take place
along with other effluents of the factory.
during the above operations are as follows:
Reduction of chromate
+ 6FeS0,
+ 7 H,SO,
+ 3Na,SO,
-I- 4H,SO,
-+
4Na,SO,
+
+ 4&O
Na,SO,
IS:9841-1981
Precipitation with lime
Cr,(SOJ,
+ 3Ca(OH),
-+
2Cr (OH),
+ 3CaS0,
Fe,(SO.&
+ 3Ca(OH),
2Fe (OH),
+ 3CaS0,
+ 3S0,
-t 2H+ -+
2Cr+-++ + 3SO,--
-1 HZ0
The reaction takes place quite rapidly at low pH (2 to 3). The SO,
present in the flue gas helps in attaining the low pH of this order; under this
condition even a small percentage of SO, is able to reduce the hexavalent
chromium.
In this arrangement
the problem
of air contamination
is also
reduced due to utilization
of SO, and SO,.
The resulting trivalent chromium as chromium
sulphate is much less
To fully overcome the toxicity problem,
it is necessary to convert
toxic.
soluble chromium sulphate into chromium hydroxide atpH 10 to 11 through
the addition of alkali as suggested in 4.3.7.
However, to further reduce the
cost of disposal, the ammonia containing
waste water itself may be utilized
as an alkali
to bring about
the precipitation
of chromium
hydroxide.
Effluents from fertilizer plants happen to be rich in plant nutrients
and can
be a secondary
source of fertilizers.
These effluents can, therefore, after
suitable treatment,
be applied on land for irrigation with the prior permission
of local authorities.
Experiments
have shown that the etfluents from fertilizer plants can be usefully employed to raise various crops and vegetables
due to their high nitrogen and phosphorus
contents.
4.3.8 Cyanide - Depending on the process and raw material, cyanides
are sometimes encountered
in the fertilizer factory effluent.
Usually cyanide
containing
effluents are completely segregated from other waste waters and
are treated or disposed of separately.
When the cyanide content is low, the
effluent can be discharged at a controlled
rate along with the other waste
water, so that cyanide content of the final effluent does not go beyond specified limits.
When the cyanide content of the effluent is comparatively
high,
some suitable treatment is required.
32
AND-/OR
STEAM
ACIDIC
SODIUM
SODIUM
HYDROXIDE
GAS
1
7
CYANIDE
BEARING
-STRIPPER
EFFLUENT
PARTIAL
OXIOATION
TO
CYANATE
r_
OXIDATION
TO NITROGEN
DISPOSAL
i_
FK.
COMPLETE
_?.?PO_S!J-
__
-t 2 NaOH
-+
.:- NaCI.
soda
cyanogen
NaCNO
chloride
is converted
into
+ HZ0 + NaCl
+ 4NaOH
+ 6NaCl
+ N, +
2H,O
IS : 9841 - 1981
present in fertilizer factory waste water normally do not require any special
treatment.
Natural dilution by the other waste water from the factory is
sullicicnt to bring down the level ofsulphides
within specified limits. SulphiJcs are present in acidic pH range as hydrogen sulphidc
and in ALaline
Hydrogen sulphide is usually removed by acr;tpII range as sulphidc salts.
lion process in the acidic pH range. In this process hydrogen sulphidc removal
Sometimes
chemical
oxidation
by
15 by stripping rather than oxidation.
dosinS chlorine is also resorted to for removing sulphides from effuents.
4.3.9.1
Sulphidc\
can
bc prccipitatcd
also
chemically.
CARBONATE
-mz--l
FLUORIDE
PHOSPHATE
AN0
)
EFFLUENT
I-I(,.
I I
FLUOK~E
LIME
FIRST
STAGE
REACTION
TANK
SECOND
STAGE
REACTION
TANK
In the former case, in the first stages the effluent is treated with chalk or
finely divided calcium carbonate at a pH of about 3.0. The requirement
of
calcium carbonate is 3 to 3.5 g for I g of F and 0% to 0.7 g for I g of PO,.
The following reactions are believed to take place:
H,SiF,
?H,PO,
-+ SiO, + 3C0,
+ Ca ( H,PO,
):: +
H,O
-t H,O
i- CO,
In the above reactions, almost all the fluorides arc precipitated ac calcium
fluoride.
Silica is also precipitated
out.
However, most of the phosphates
During the second stage
remain in solution as monocalcium
phosphate.
treatment,
the product of the first stage is further treated with lime at a pH
33
1s:
of about 8.5. In this reaction. calcium hydroxide requirement
for I g of residual F and 1.0 to 1.1 g for I g of residual PO,,.
It is believed
9841 - 1981
is 2. I to 2.3 6
reaction
takes
place:
H,SiF,
3Ca ( H,PO,
+ 3Ca ( OH j2 -+ 3CaF,
)z +
-t SiO, -t 3H,O
7Ca ( OH )z -+ 2Ca,OH
( PO, )s +
I2H,O
In the second stage. residual fluorides and phosphates from the first stage
arc converted into insoluble caicium fluoride and calcium hydroxy apatite at
The overall fluoride and phosphate
/IH around 8.5 and precipitated
out.
removal efficiency is above 99 percent in the above two stage treatment.
In double lime treatment,
lime is used in place of chalk or powdered
calcium carbonate as indicated earlier in the two stage treatment.
The efhuent after the second stage reaction is transferred to a settler for
the removal of fluoride and phosphate
precipitates
and the overflow water
is discharged.
The settled sludges are removed periodically and dumped or
used as fill for low lying areas.
4.X10.1 Where by-product
precipitated chalk from ammonium
sulphate
produced by Merseburg process is used for preliminary
treatment, the chalk
should have a minimum optimum ammonia level or preferably it should be
fret from ammonia.
4.3.11 Srwuge Ejhent .~ The waste water from toilets and other sanitary
facilities in the factory area has high biochemical
oxygen demand ( BOD )
and contains suspended solids. The sewage effluent is segregated from other
industrial wastes and treated for removal of BOD and suspended solids. The
volume of the eflluent is normally comparatively
low. The general practice
Howis to treat these effluents in oxidation ponds or by aeration processes.
ever, depending on the level of HOD, these waste waters may be subjected to
partial BOD removal by any conventional
practice and discharged along
with the other treated industrial
waste water so that the BOD value of the
final effluent does not go beyond specified limits.
4.4 Sampling and .4nalytical Control - In order to observe the performance
of the ctlluent treatment units and also to control the plant operating system
etfcctivcly. suitable instrumentation
for recording pollutants and other physical characteristics
( namely temperature,
pressure. flow of effluents, quantny
of treatment chemicals. etc ) are required to be incorporated
into the etlluent
treatment
process design. so that input and output conditions
of cfhucnt
Where suitable automatic contreatment
units can be assessed properly.
tinuous monitoring
of pollutants in the effluents cannot be provided. regular
sampling and anaI!sis of the pollutants
necessary for the control of operation
In such a case, the frequency of sampling and analysis
arc to be conducted.
35
IS :9841-
1981
will depend on the process plant operating conditions but a minimum of two
composite samples should be analysed daily. In the case of final effluent
discharged beyond the factory boundary limit, a suitable arrangement for
recording the volume and proper sampling of the final effluent is to bc made
Installation of an automatic pollutant monitoring and recording system for
final effluent of the factory is very advantageous and an endeavour should be
made to install these instruments wherever possible. Similarly, a composite
sample of the receiving water should also be analysed daily. In case some
other industries are located on the upstream of the river and they also discharge some effluents to the same river. sampling and analysis of the receiving water should be done. both from the upstream and downstream of the
effluent outfall. This will indicate the contribution to pollution by the fertilizer industry concerned.
4.5 Waste Utilization - Apart from the utilization of waste waters and reuse
of treated effluents for conservation of water as well as for other purposes,
recovery of usable products present in this waste water has gained importance
in recent days. The main recoverable products from waste waters of fertilizer industries are ammonia, urea, carbon, fluoride, gypsum, phosphate,
chalk, etc, depending on the product manufactured and the process adopted.
4.5.1 Ammonia-The processes
commonly used for the recovery of ammonia
from ammoniacal waste waters are steam stripping and ion exchange system.
Steam stripping of ammonia is suitable for ammoniacal effluent containing
high concentration of ammonia with comparatively low volume. The stripped ammonia gas is either absorbed in acid to form ammonium salts or
condensed to form ammonia liquor which is recycled in the process itself.
In the case of ammoniacal waste waters containing low concentration of
ammonia, ammonia can be recovered using a cation exchange system regenerated with acid to produce ammonium salt solution. This process is
more suitable where already a secondary ammonium salt manufacturing
facility exists.
4.5.2 Urea - In spite
ring process, substantial
into the waste waters of
urea from these effluents
of improvement in the design of the urea manufactuamount of urea along with ammonia finds its way
urea plant. The different methods of recovery of
are as follows:
Scrubbing urea dust from prilling tower exhaust vapours and recovering this urea as per process mentioned in (b) above.
36
is:
9x41-
1981
IS : )x41- 1981
individual
clllucnt treatment
units are Icd to a mixing pond.
lhc uncon
taminatcd effluents which do not require any treatment
also flow to this
mixing pond.
It is preferable to give sulficient detention time in Ihi, mixing
pOJld
for
CqualiZatiOIi
and
alSO
t0
effect
5eCOndary
settling
Of sM;)Cl&xi
The overflow from this final mixing pond passes to the elllucnt drain
matter.
leading to the receiving waters.
It may be clearly understood
that the treated effluents in the effluent drain conform to IS : 2-M* and therefore cannot
in case the drain
passes through a
normally be used as raw water source.
locality where there is possibility
of use of this water as raw water source
of the drain from the
by the inhabitants
and cattle. suitable protection
approach of the pcoplc and cattle with proper warnings has to be made. III
some
cases
it is preferable
to discharge the treated effluents through a pipcWhen
all the characteristics
of the individual
lint to the receiving water.
effluent streams of the process plants are properly asscsscd, the effluents
discharged from effluent treatment units also can be evaluated
with respect
to the extent of treatment necessary during the planning and designing stage
of the efnuent treatment
plants.
The final effluent characteristics
can be
predicted and made to comply with the requirements
prescribed
by the
regulatory authorities.
APPENDIX
( Clause 0.5 )
REFERENCES
ALAGAKSAMY ( S R ), BHALEKILO ( B B ) and JZAJAGGPALAN
wastes from fertilizer plants.
Irdfan J. Environ. 15, 1 ; 1973 ;
( R J ) and
AUSTIN
water.
( R E ).
BAUMANN
nar,
VANSE
Kansas
city,
( E H ).
Waste
On removal
USA 197 1.
Chemical Coagulation
Conference.
of ammonia
Purdue
Univ.
by air stripping
limits
for industrial
effluents
discharged
(first revision )
fertilizer industry
fertilizer industry
into
inland
(first revision )
(first
revision j
( S ) Treatment
52.
of refinery
I-eb.
1951; 272.
-- EPA
Design
problems
Society
surface
of
waste
semi-
in fertilizer
of London,
waters
(/;r,sr
IS : YH41 - 1981
5.
use
and
of efBucnts
presented
<
s.
~AT~~~AC~~AHYA
( <; s
), SAKlcAK
( c
&I
IA
( 1% K
).
~hOSphdtC
Idper
POhiiC~!l
cnrltr01 in 1)~~
( s K ), BtIATrACHAIIYA
( c; s ) :tnd I)t,TrA
( u K )_ Kenl(~\al <,!
from nitrogcnc,us effluent. Tr~,lr~~jlIO ; 3: 1 : 1973 ; ??_I.
I<IiAYTACtIAHYA
nitrogen
IO.
1.) ) alld
hoc.
cII\P~~\.II
. 62
bINbllAM ( E C ). Solutions
Expert
Group
meeting
on
for minjmum
minimi7ir,g
pollution
pollution
in nitrogen
from
Industry.
fertilii-cr
Lhl
plants.
110
llclsinhi
Aug. 1974.
1 I.
12.
HINC~IIAM
( 1-t C ) and CIIUIJHA
( Ii C ). :\ unique closed cycle water
s)stcm Iljr lil~
ammonium
nitrate producer
using Chem-scps continuous
counter current 1ut1
exchange.
Proc. of 32nd Internattonll
Water Conference of the Engs SOC of \\ ei:
Penn. Pillsburg, USA I\lov 1971.
BHIN(;UA~U~+( G ).
J.
lJt~t~rrft.r
Poll
Ahr.
On nitriticatioii
17 , I964 ; 18.
and dcnitrification
111 SeWcige
treatment.
13.
14.
cyamdc
CHATT~RJLI: ( D 1) ), SRIVASTAVA ( A C ) and DUTTA (, B K ). Hydrogen
Technoi. 13 ; 4 ; I)76 :
from weak aqueous
potassium
cyanide
solution.
removal
273.
15.
16.
( G
Advanced
17
( R L ).
On air stripping of ammonia
.I. Amer. WL)IPT wkr Assn. 60 ; 1968 : 84~
CULP
reclamation.
18.
19.
DE LOKA ( F Y ) and MASIA ( A ). Influence of effluent standards on the economics of alternate waste water treatment designs ; UNIDO Expert Group meeting on
minimizing pollution from fertilizer plants. Helsinki Aug 1974.
20.
DJJKSAKA
( F
).
Measures
39
IS : 9841 - 1981
1jrr.1 r,z ( 13 K ).
ted in ,411 India
Ma> IOSO.
30 ( 121 ) Jun
4t , 13X ) July
tIowI.
Iroc.
Removal
Symposium
of ammonia from
Fcdcral Kegistcr
72 ( I975 ) ; JI
Ih ( 1976 ).
or:
fertilizer
Treatment
Efllucnt
.?I ( 6X )
( I I ) Jan
April S ( 1974 )
I6 ( 1970 ) ; .II
: 30 ( 9 ) Jan
C9s ) $1~1~
II\.<;
( 4 ).
l%>llution
f-rtm
Group meeting on minimrling
JOIINSON
( W
denitrification.
iertllirer
pollution
1-l I 1975
IO ( 1970
plants
in Bangladesh.
UNIDO
1:xpcrt
from fertilizer plants Helsinki,
Aug. 1074.
) and S~III~~~IYIK
( G J ).
Nitrogen
removal
.1. IV~o/f,. I+,//. (;,,rff.
/;t,c/. 41 ; I971 ; 1x45.
by nitrificatlon
~.IIJTAK
BILA
( <i ).
Removal ofcyanidc
and chromium.
Environmental
Handbook
vol 1 Mater pollution.
Chilton
Book Co. US.4 p 1365 1782.
( Ii R ) and
~~hnol
3
industry.
industry
L)u.rr~
(
1966
:4 :
i:
1.
Part I. t~-\I
Report
Tech J.
Engineers
1079
!3 K ). A study of etlluents 01
; 65 Spl. issue. Seminar on wastes
and
t-crtlllzer
Sindri Fertillret
and dIlucnts
1n
Roy ( G S ), I~I-I,\~I~.I~ACC~AI~YA
( G S ) and Dutta ( B K ),
rreatment
and disposal
of effluents from fertilizer
industries.
Techr~ol 7; 3 ; 1970 ; 193.
Paper presented
in seminar
on Water
pollution and industrial
waste treatment
in Bangalore,
Dee
190q.
SRIVAS~AVA
( A c ) and
tries by an ion exchange
cual and coal chemicals.
The Water
bHALI.EY
UNIDO
Helsinki.
( Prevention
( L ).
Modern
Expert
Ciroup
Aug 1074.
L)UTTA
( I) K ). Ammonia
recovery from coke oven indusprocess, T~C/VIO/ 7 ; 4 ; 1070 ; 66 spl. Issue on seminar
on
Nov. 1968.
Xr Control
of Pollution
) Act.
1974 Govt.
of India.
40
plants.
plants.
IS : 9841- 1981
( Continued from page 2 )
Members
SHRI R. M. SHAH
Representing
SHRIN. K. SHARMA
Deputy Director ( Chem ), IS1
Waste Treatment
Methods
Subcommittee,
CDC 26 : 1
Convener
SHR~A. RAMAN
National Environmental
Engineering
Institute ( CSIR ), Nagpur
Research
Members
41
IS : 9841- 1981
Representing
Members
SHKI S. GUPTA
DK H. S. MATHAK~~ ( Alfernate
)
SHRI R. V. KADAM
SHRI N. V. VASHI ( Alfernare )
SHRI K. R. KRISHNASWAMI
SHRI V. N. LAMRU
SHKI V. V. JOSHI ( Allenrate
)
SHRI A. K. MAJUMDAR
SHRI U. C. MANKAU (Alternate
)
SHRI S. V. MANI
SHRI S. R. LUTHRA ( Alfernate
)
SHRI V. S. MORE
SHKI PAKAMJW SINGH ( Alternate
SHIU D. V. S. MURTHY
DR G. K. KHARE ( Akmate
)
SHRI R. NATARAJAN
SHRI AMI.I. S. DESAI ( Alternute )
DR V. PACHAIYAPPAN
DK R. N. TRIVEDI ( Alternate
)
Jh R. PITCHAI
SIIRI
H.
S. PrJRI
Paramount
and Control
of
Dorr-Oliver
of Water Pollu-
Ltd, Bombay
& Control
DUTTA
) India
Members
SHRI G. S, RAY ( Alternate
to
Shri B. K. Dutta )
DR R. N. CHAK~UBARTY
DR S. K. GUPTA ( Alternafe )
SHRI P. P. CHANDHNA
SHRI V. CHARANDAS
SHRI M. D. PATEL ( Affernate
SHRI L. M. CHOUDHRY
SHRI
M. L.
Universal Enviroscience
PRABHAKAR ( Alternate
& Control
)
( Conrinued
42
on page
43 )
IS:9841- 1981
( Continued from page 42 )
Members
Representing
Directorate General
New Delhi
SHRI K. P. DOHARE
SHRI K. V. SAMPPTH ( Ahvrate
of
Technical
of
Development,
Water
Pollu-
Ltd. Durgapur
SHRI T. P. CHATTERJEIZ
( Alternate )
Ion Exchange ( India ) Ltd, Bombay
SHRI V. V. JOSHI
SHRI S. K. BHA~ACWARYY~ ( Alternate )
Indian Exolosives Ltd. Kanuur
SHRI S. MALLICK
_
33~1 T. N. MEI~ROTRA( Alternate )
Gujarat Water Pollution Control Board, GandhiPROFR. S. MEF~TA
nagar
Hindustan Dorr-Oliver Lid, Bombay
SHRI R. NATARAJAN
Shriram Chemical Industries, New Delhi
SHARIA. G. NCNE
Hindustan Lever Ltd, Bombay
DR R. K. NIYO~I
SHRI S. K. SU~BAR~~..I~X
( Alternate )
The Fertilizer Association of India, New Delhi
DR V. PACHAIYAPPAN
DK R. N. TKIVEDI( Alternare )
The Fertilizers Rr Chemicals,
Travancore
Ltd.
SIIRI D. PANIGRAHI
Udyogamandal
SHKI N. J. JOSLYH( Alternate I )
DR A. K.
GUPTA
& Control
33
Research
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