FOR BIS USE ONLY Doc: CHD 32 (1544)C

September 2010

BUREAU OF INDIAN STANDARDS

Draft
Indian Standard

SOLID WASTE MANAGEMENT IN THE FERTILIZER INDUSTRY – CODE OF

PRACTICE

ICS NO. 13.030.10; 65.080

(Not to be reproduced without the permission of BIS or used as STANDARD)

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Last date of receipt of comments: 31-12-2010
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FOREWARD
(Formal clauses to be added later on)

Indian Fertilizer Industry is the third largest producer of fertilizer in the world. In India, there
are about 56 major nitrogenous and NP/NPK, and 72 single super phosphate plants having
capacity of 12.3 million tonnes of nitrogen and 5.7 million tonnes of P2O5. The production of
fertilizer from such large capacity does release wastes into the Environment in various form and
is bound to be significant. Consequently, efforts towards Environment Protection to minimize
the waste produced through recycling/utilization and eliminating the use of toxic substance to
make fertilizer production environmental friendly is a pre-requisite.

1. SCOPE

This standard describes the guidelines for disposal and use of various waste generated by the
fertilizer industry. Source of generation and characteristics of these wastes have also been
prescribed.

2. REFERENCE

The standard listed below contains provisions which through reference in this text constitute
provisions of this standard. At the time of publication, the edition indicated was valid. The
standard is subjected to revision and parties to agreements based on this standard are encouraged
to investigate the possibility of applying the most recent edition of this standard indicated below:

IS No. Title
10153: 1982 Guidelines for Utilization and Disposal of Fly Ash

3. CLASSIFICATON OF VARIOUS SOLID WASTES IN FERTILIZER INDUSTRY

Wastes generated from the fertilizer industry are broadly classified as given below based on their
source of generation.

a. Spent Catalyst
b. Carbon Sludge
c. Arsenic Sludge
d. Chromium Sludge
e. Waste Oil
f. Acid/Alkaline Waste
g. Fly Ash
h. ETP Sludge
i. Sulphur Sludge
j. Hydrofluosilicic Acid (Fl2SiF6)
k. Phosphogypsum
l. Lime/Lime Sludge
m. Others like Scrap, Silica, Alumina Balls
n. Spent Carbon
o. Molecular Sieves

4. UTILIZATION/DISPOSAL OF SOLID WASTE

Waste generated should be handled and disposed off suitably as given in col.4 of Table 1.

TABLE 1: GENERATION AND RECOMMENDED USES OF SOLID WASTES FROM

THE FERTILIZER INDUSTRY

Sl.
No. Solid Waste Sources
(1) (2) (3)
i) Spent Catalyst The process of manufacture of
ammonia involves several steps. In
almost all the step catalysts are used.
Catalyst is also used in synthesis of
sulphuric acid. The name and
composition of the catalysts used in
the manufacture of ammonia and
sulphuric acid are given in Annex A.
These catalysts have different life.
ii) Carbon Slurry The carbon waste is basically
generated in ammonia plants based on
either fuel oil or coal. In ammonia
plants based on Shell partial oxidation
process for gasification of fuel oil
during gasification of oil about 2%
Utilization / Disposal
(4)
Spent catalysts should preferably
be sold to only CPCB/SPCB
authorized waste processors for
metal recovery and re-use. If
authorized waste processors are
not available, it may be stored in
the plant premises as per CPCB
guidelines and in accordance
with the Hazardous Waste
Management Rules.
Carbon should be recovered
from carbon slurry and either
recycled or dried in lined
lagoons and sold for utilization
in downstream industries like
rubber, dyes etc.
 Sl.
No. Solid Waste Sources Utilization / Disposal
(1) (2) (3) (4)
carbon is left unburnt. Thus a large
quantity of carbon is produced every
day.

iii) Arsenic Sludge Plants based on Vetrocoke process of Arsenic sludge should be
CO2 removal generate arsenic disposed of either through
contaminated effluent and have an secured landfill or specially
inbuilt recycle system. The typical designed landfill at site or stored
composition of arsenic sludge is given in sealed RCC tanks within the
in B–1. plant premises.

In all the CO2 removal processes, Vanadium Sludge is treated with

bottom sludge from the Solution
preparation pit will be contaminated
with Vanadium (used for Passivation
in the system) and shall be neutralized
with Ferrous sulfate to get V5+ Conc.
Within limits before disposal.
ferrous sulphate in a pit to
convert V3+ to V5+ which is non
hazardous and the solution is
sent to guard pond in small
doses.

All plants on arsenic based CO2

removal process are either closed or
have switched over to non-arsenic
based system”. Hence, there is no
fresh generation of Arsenic Sludge.
iv) Chromium Sludge Plants using chromate based cooling Chromate sludge being toxic
water treatment system produce should be stored in high-density
chromate sludge. The typical polyethylene lined/concrete
composition of chromium sludge is lagoons and encapsulated or
given in B–2. covered with greenery. The
sludge may also be disposed in
All plants have switched over to non- Secured Land Fill (SLF) or
chromate cooling water treatment. Chromium may be recovered
Hence, there is no further generation from sludge by vacuum
of chromium sludge. evaporation process.
v) Waste Oil Waste oil is by and large collected The waste oil generated should
from spillages, leakages and washings be processed and reused in the
from oil unloading, storage, pumping plant or sold to CPCB/SPCB
section, pumps and compressor bays. authorized agencies. However,
the waste oil generated may also
be stored in sealed steel drums at
an allocated location within the
plant premises.
Sl.
No. Solid Waste Sources Utilization / Disposal
(1) (2) (3) (4)
vi) Acid/Alkaline By and large the acid and alkaline Acid/Alkaline wastes produced
Waste waste is generated in demineralization should be utilized within the
plants and acid plants. plant itself for pH adjustments of
effluents.
vii) Fly Ash Some of the fertilizer plants have Disposal and use of fly ash
captive power plant based on coal. should be done as prescribed in
Such plants generate fly ash and it is IS: 10153 or MOEF Notification
recovered through electrostatic on utilization of fly ash.
precipitators. Typical analysis of Fly
Ash is given in Annex C.
viii) Effluent Effluent Treatment Plant Sludge is Recoverable material may be
Treatment Plant produced from effluent treatment plant recovered and sludge thus may
Sludge be disposed off in Lagoons.
ix) Sulphur Sludge In the sulphuric acid plant, sulphur Sulphur may be utilized as filler
sludge is the major waste product. The in manufacturing of complex
typical composition of sulphur sludge fertilizers/SSP fertilizers. It can
is given in B–3. also be used as construction
material for making roads, civil
structures.
x) Hydrofluosilicic In the manufacture of phosphoric acid The hydrofluosilicic acid may be
Acid (H2SiF6) and single super phosphate, fluorine re-circulated for acidulation of
present in the rock phosphate is rock phosphate or converted to
released on acidification. The released AlF3/Cryolite/Na2SiF6.
fluorine is scrubbed with water to
generate hydrofluosilicic acid, which
is a strong acid.
xi) Phosphogypsum Phosphogypsum is the by-product in Phosphogypsum should be
the manufacture of phosphoric acid. utilized for cement production.
For every tonne of phosphoric acid It may also be used for soil
manufactured, approximately 4.5-5 conditioning or making gypsum
tonnes of gypsum is generated. tiles/boards, etc.
Typical analysis of Phosphogypsum is
given in Annex D.
xii) Lime/Chalk Lime/Lime sludge, is generated during The lime-sludge so generated
Sludge the manufacture of ammonium should be used by either mixing
sulphate from Phosphogypsum. with ammonium nitrate to form
CAN (25% N) or used in cement
production or used for
neutralizing phos-acid plant
effluent.
Sl.
No. Solid Waste Sources Utilization / Disposal
(1) (2) (3) (4)
xiii) Other Wastes like Solid waste like silica generated in the Waste should be used as filler,
Silica, Scrap, fluorine scrubbing system during the while the scraps (metal, paper,
Alumina Balls formation of hydrofluosilicic acid. wood. Etc) should be sold, if so
desired, to the authorized waste
processors only for recovery and
reuse.

Alumina balls are non toxic in

nature and are mostly recycled.
The fines with catalyst should be
sold to authorized recyclers/re-
processors.
xiv) Spent Carbon Spent carbon is generated from The spent carbon should be
activated carbon filters in CO2 removal analyzed for hazardous
section. constituents, if any. Mostly it is
non hazardous in nature and
should be sold for reuse to
outside agensies.
xv) Molecular sieves Gas purification section It is non hazardous and can be
land filled.

ANNEX A
CATALYSTS USED IN AMMONIA MANUFACTURE AND THEIR COMPOSITION

Sl. No. Name of the catalyst Composition of the Catalyst wt %

1. Hydrodesulphurisation Catalyst
a) HR–101 MoO3

b) HR–306C CoO, Fe2O3, Na2O, Al2O3

2. Desulphurisation Catalyst
a) 32–4 ZnO and binder, CoO

b) 41–3 MoO3, Al2O3

3. Primary Reforming Catalyst Oxides of Ni, Si, Mg, Al, K
a) 46–1 NiO – 19–35%

b) 46–4 NiO – 15–35%

46–6 NiO – 15–35%
4. Secondary Reforming Catalyst
a) C–15–1 Cr2O3, Al2O3, Zn

b) C–11–4 NiO, Refractory support of Al2O3

5. High Temperature Shift Conversion Catalyst
a) C–12–l Cr2O3 – 8% (approx.)
Fe2O3 – balance

b) CDC–93C–HT Fe2O3 – 85–9O%

Cr2O3 – 7–9%, CuO – l–2%
6. Low Temperature Shift Conversion Catalyst
a) C–18–HC CuO – 38%, ZnO – 42%

b) LSK CuO – 19.6%, ZnO – 31.7%

c) CD–LT–21–A CuO – 25–27%, ZnO – 25–27%

R2O3 – 38–40% (Al2O3+Fe2O3)
7. Methanation Catalyst
C–13–4 Ni – 20+/-2%
8. Synthesis Catalyst
a) C–T3–l Fe2+, Fe3+, K2O, CaO, Al2O3

b) KM1–R Fe3+ – 90%

Balance – K2O, CaO, Al2O3

c) KM1 Fe3+ – 90%

Balance – K2O, CaO, Al2O3
9. Sulphuric Acid Synthesis Catalyst V2O5 = 6%
ANNEX B
 B–1: A Typical Analysis of Arsenic Sludge

Composition Value %
As2O3 12.0
As2O5 11.5
Fe2O3 15.5
K2O 22.3
Moisture 38.7

B–2: Typical Characteristics of Chromium Sludge

B–2.1: Physical Characteristics

Nature : Sludge, Slimy, Slightly alkaline

Colour : Light grey
Solubility : Insoluble in water
Odour : Odourless
Combustibility: Non-combustible

B–2.2: Chemical Characteristics

Characteristic (%) Average Values (%)

Loss on ignition 33.65
Acid insoluble as Silica 16.56
Iron as Fe2O3 1.49
Chromium as Cr2O3 17.99
Calcium as CaO 18.74
Magnesium as MgO 8.50
Phosphate as P2O5 1.52
Zinc as Zn 1.55

B–3: Typical Composition of Sulphur Sludge

Composition Value %
Moisture 1.04
Organic Matter 3.15
Ash 50.11
Sulphur as S 45.7

ANNEX–C
 TYPICAL ANALYSIS OF FLY ASH

Properties Rangc (% w/w)

Combustibles 8.0 to 20.0
SiO2 48.0 to 61.6
Al2O3 15.0 to 20.0
Fe2O3 8.0 to 11.0
TiO2 1.3 to 1.7
CaO 0.1 to 0.4
MgO 0.20 to 1.4
Na2O 0.41 to 0.45
K2O 0.61 to 0.80

ANNEX–D

TYPICAL ANALYSIS OF PHOSPHOGYPSUM

Sl. No Parameter % w/w

1 Free Moisture 20 (max)
2 Purity as CaSO4 2H2O 94 – 96
3 Silica & Insolubles 3 (max)
4 Fe2O3 & Al2O3 5 (max)
5 CaO 31.0 – 32.5
6 MgO 0.10
7 Na2O & K2O 0.50
8 Total P2O5 1.00 (max)
9 WS P2O5 --
10 Total SO4 43.5 – 44.7
11 Fluoride 0.4 – 0.6 (as F)
12 Chloride as Cl 200 (max)