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तकनीकी समितत : पयावरण सरषण वव ष समितत, सीएचडी 32
रा तरता
1 सीएचडी 33 र सभी सद य 2 सीएचडी 33 र पनल र सभी सद य 3 चच रखन वाल अ य िनराय
महोदय(य),
रपया िन निलिखत मसददा रा त रर
सीएचडी 33 (2277) सी उव रर उयोग म ठोस अपििटख रबधन –रीितसहहता
रपया इस मसदद रा अवलोरन रर और अपनी स मितय यह बतात हएए भ िर यहद यह मसददा रा रीय मानर र प म ररािित हो तो इस पर अमल ररन म आपर यवसाय अववा रारोबार म या रहठनाइय आ सरती ह।
स ितत जननज की तति तत 01 02 2016.
स मितय यहद रो हो तो रपया अधोह तारत त रो उपरिलिखत पत पर सल न ोोमटट म भ ।
यहद रो स मित रा त नही होती ह अववा स मित म रवल भााा सब धी टएहट हए तो उपरो त रलख रो यवावत अितम प द हदया ाएगा। यहद स मित तरनीर ररित र हए तो िव ाय सिमित र अ य र परामि स अववा उनर इ छा पर आग र राय वाही र िलए िव ाय सिमित रो भ ान र बाद रलख रो अितम प द हदया ाएगा।
ध यावाद, भवदीय
सल न उपरो तिलिखत
(डा आर र झा) वञािनर एो एव रमएख (रसायन)
यपक पचरचय न िस य हमारा सदभ सीएचडी 33/टी (2277)सी हदनार : 01 01 2016
DRAFT IN WIDE CIRCULATION
DOCUMENT DESPATCH ADVICE
Our Ref : CHD 33/ DOC : (2277) Date : 01 01 2016
TECHNICAL COMMITTEE: Solid Waste Management Sectional Committee, CHD 33 _______________________________________________________________ ADDRESSED TO : 1. ALL MEMBERS OF : a) Solid Waste Management Sectional Committee, CHD 33 b) All Interested Dear Sir(s), Please find enclosed following document : CHD 33(2277) C SOLID WASTE MANAGEMENT IN THE FERTILIZER
INDUSTRY – CODE OF PRACTICE Kindly examine draft standard and forward your views stating any difficulties which you are likely to experience in your business or profession, if these are finally adopted as National Standard. Last date for comment: 01 02 2016. Comments, if any, may please be made in the format as given overleaf and mailed to the undersigned at the above address. In case no comments are received, we would presume your approval of the documents. However, in case we receive any comments on the document, the same shall be put up to the Sectional Committee or necessary action. Thanking you,
Yours faithfully,
Encl: As above (Dr. Rajiv K Jha)
Scientist F & Head (Chemicals)
DOC : CHD33 (2277)C
उवरक उयोग म ठोस अपशि ट बधन –रीतिसबहििा
Draft Indian Standard
SOLID WASTE MANAGEMENT IN THE FERTILIZER INDUSTRY – CODE OF PRACTICE
ICS 13.030.10; 65.080
© BIS
B U R E A U O F I N D I A N S T A N D A R D S MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG
NEW DELHI 110002
Price Group
Solid Waste Management Sectional Committee, CHD 33
FOREWORD
[Formal Clauses to be added later]
Indian Fertilizer Industry is the third largest producer of fertilizer in the world with 159 plants presently in
operation. The production of fertilizer from such large capacity does release wastes which are significant
to cause adverse environmental impacts. Consequently, efforts are needed to minimize the waste
produced through recycling, reuse, elimination of the use of toxic substances etc. Such efforts would help
reduce/eliminate potentially adverse environmental impacts. It will also make fertilizer manufacturing
more environment friendly.
There is a need to develop processes for the waste generated which can be suitably utilized in the
downstream industries such that the same is consumed in the related manufacturing cycles. This may also
help in conserving the natural resources including energy conservation.
This Indian standard describes guidelines for disposal and use of solid wastes generated by fertilizer
Industry which should be implemented in conjunction with relevant notifications of Ministry of
Environment, Forestand Climate Change (MNEFCC) Notificationand Guidelines of Central Pollution
Control Board (CPCB). Wherever this standard mentions about selling Solid Waste to authorized
agencies, it means that they shall be authorized by designated agencies.
DOC : CHD33 (2277)
Draft Indian Standard
SOLID WASTE MANAGEMENT IN THE FERTILIZER INDUSTRY – CODE OF PRACTICE
1 SCOPE
This standard describes the guidelines for disposal and use of various wastes 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 fromthe fertilizer industrybased on their soruce of generation are given below
a. Spent Catalyst
b. Carbon Sludge
c. Arsenic Sludge
d. Chromium Sludge
e. Acid/Alkaline Waste (solid)
f. Fly Ash
g. Effluent Treatment Plant (ETP) Sludge
h. Sulphur Sludge
i. Phosphogypsum
j. Lime/Lime Sludge
k. Others like Scrap, Silica, Alumina Balls
l. Spent Carbon
m. Molecular Sieves
n. Spent resins
o. Zinc mud
4 UTILIZATION/DISPOSAL OF SOLID WASTE
Waste generated should be handled and disposed off suitably as given in col.4 of Table 1.
Table1 Generation and Recommended Uses of Solid Wastes from the Fertilizer Industry (Clause 4)
Sl.
No. (1)
Solid Waste (2)
Sources (3)
Utilization / Disposal (4)
i) Spent Catalyst The process of manufacture of ammonia
involves several steps. In almost all the
steps 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. The
composition given are typical and vary
from vendor to vendor. These catalysts
have different life.
Spent catalysts should preferably be
sold to only 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 the authorized guidelines and in
accordance with the Hazardous
Waste Management Rules. Spent
synthesis catalyst can be disposed-
off as landfill provided it does not
contain heavy metals carryover
from upstream sections.
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 during
gasification of oil,about 2% carbon is left
unburnt. Thus a large quantity of carbon
is produced every day.
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.
iii) Arsenic Sludge Plants based on Vetrocoke process of CO2
removal, generate arsenic contaminated
effluent and have an inbuilt recycle
system. The typical composition of
arsenic sludge is given in B–1.
In all the CO2 removal processes, 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+
Concentration within limits before
disposal.
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.
Arsenic sludge should be disposed
of either through secured landfill or
specially designed landfill at site or
stored in sealed RCC tanks within
the plant premises.
Vanadium Sludge is treated with
ferrous sulphate ina pit to convert
V3+
toV5+
which is non hazardous
and the solution is sent to effluent
treatment plant in small doses.
iv) Chromium Sludge Plants using chromate based cooling water
treatment system produce chromate
sludge. The typical composition of
chromium sludge is given in B–2.
Chromate sludge being toxic should
be stored in high-density
polyethylene lined/concrete lagoons
and encapsulated or covered with
Sl.
No. (1)
Solid Waste (2)
Sources (3)
Utilization / Disposal (4)
There is no further generation of
chromium sludgeas all the plants based on
chromate based treatment system have
switched over to non-chromate cooling
water treatment.
greenery. The sludge may also be
disposed in Secured Land Fill
(SLF) or Chromium may be
recovered from sludge by vacuum
evaporation process.
v) Acid/Alkaline
Waste (solid)
By and large the acid and alkaline waste is
generated in demineralization plants and
acid plants.
Acid/Alkaline wastes produced
should be utilized within the plant
itself for pH adjustments of
effluents.
vi) Fly Ash Some of the fertilizer plants have captive
power plant based on coal. Such plants
generate fly ash and it is recovered
through electrostatic precipitators. Typical
analysis of Fly Ash is given in Annex C.
Disposal and use of fly ash should
be done as prescribed in IS: 10153
or Notification on utilization of fly
ash issued by the regulating
authorities.
vii) Effluent Treatment
Plant Sludge
Effluent Treatment Plant Sludge is
produced from effluent treatment plant.
Recoverable material, if
economical, may be recovered and
sludge thus may be disposed off in
Lagoons or may be either utilized
as manure or used as landfill in low
lying areas.
viii) Sulphur Sludge In the sulphuric acid plant, sulphur sludge
is the major waste product. The typical
composition of sulphur sludge is given in
B–3.
Sulphur may be utilized as filler in
manufacturing of complex
fertilizers/Single Super Phosphate
fertilizers. It can also be used as
construction material for making
roads, civil structures.
ix) Phosphogypsum Phosphogypsum is the by-product in the
manufacture of phosphoric acid. For every
tonne of phosphoric acid manufactured,
approximately 4.5-5 tonnes of gypsum is
generated. Typical analysis of
Phosphogypsum is given in Annex D.
Phosphogypsum to be utilized as
per the CPCB Guidelines on
Management, Handling, Utilisation,
and Disposal of Phosphogypsum
generated from Phosphoric Acid
Plant (October 2014). It has been
mentioned in the guidelines that
phosphogypsum can be utilized for
cement production, soil
conditioning or making gypsum
tiles/boards, etc.
xii) Lime/Chalk Sludge Lime/Lime sludge, is generated during the
manufacture of ammonium sulphate from
Phosphogypsum or in production of
nitrophosphate fertilisers by ODDA
process
The lime-sludge so generated
should be used by either mixing
with ammonium nitrate to form
Calcium Ammonium Nitrate, CAN
(25% N) or used in cement
production or used for neutralizing
Sl.
No. (1)
Solid Waste (2)
Sources (3)
Utilization / Disposal (4)
phosphoric-acid plant effluent.
x) Other Wastes like
Silica, Scrap,
Alumina Balls
Solid waste like silica generated in the
fluorine scrubbing system during the
formation of hydrofluosilicic acid.
Waste should be used as filler,
while the scraps (metal, paper,
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.
xi) Spent Carbon Spent carbon is generated from activated
carbon filters in CO2 removal section.
The spent carbon should be
analyzed for hazardous
constituents, if any. Mostly it is non
hazardous in nature and should be
sold for reuse to outside agencies or
may be used as a landfill in low
lying areas. Spent carbon can be
used for steam generation in boiler
after mixing with coal or co-
processing in cement industries
with prior approval of
CPCB/SPCB.
xii) Molecular sieves Gas purification section It is non hazardous and can be land
filled.
xiii)
xiv)
Spent Resins
Zinc mud
Water treatment/De-mineralization Plant
In process of manufacturing of zinc
sulphate by reaction of zinc ash and
sulphuric acid.
It is non hazardous and can be land
filled or can be used for steam
generation in boiler after mixing
with coal.
Zinc mud is generated as solid cake
and disposed-off to the CPCB
approved TSDF sites.
ANNEX A (Table 1)
CATALYSTS USED IN AMMONIA MANUFACTURE AND THEIR COMPOSITION
Sl.
No.
(1)
Name of the catalyst
(2)
Composition of the
Catalyst w/w %
(3)
i)
a.Hydrodesulphurisation, (HDS) Catalyst CoO-(3-4%), MoO3-(3-4%), Al2O3-
(84-88%); Na2O-(4-5%) & Fe2O3-(2-
3%)
b. when hydrocarbon gas feedstock contains CO2
greater than4-5%
NiO-(3-4%), MoO3-(3-4%), Al2O3-
(83-87%); Na2O-(4-5%) & Fe2O3-(2-
3%)
ii)
Desulphurisation Catalyst ZnO-(89-91%); MoO3-(2.1%); binder,
balance Al2O3
iii) Pre-Reforming Catalyst
NiO-(26-35%), small amount of
Oxides of Mg,& K , balance either
SiO2 or Al2O3
iv) Primary Reforming Catalyst
NiO-(16-24%), oxides of Mg &K,
balance is either Al2O3 or occasionaly
SiO2 in some varities.
v)
Secondary Reforming Catalyst
NiO-(8-11%), small amount of K &
Na (<1000 ppm); Silica (<1000 ppm),
balance Al2O3
vi)
High Temperature Shift Conversion Catalyst Fe2O3-(85-90%), CuO-(1-3%), Cr2O3-
(6.5-9.5%),
vii) Low Temperature Shift Conversion Catalyst
a) High Copper variety CuO-(35-37%), ZnO-(35-37%),
balance Al2O3+Fe2O3
b) Low Copper variety
CuO-(25-27%), ZnO-(25-27%),
Balance = (Al2O3+Fe2O3)
viii)
Methanation Catalyst
NiO-(22-25%), balance=Al2O3+traces
of Fe2O3
ix) SynthesisCatalyst Fe2O3 (~90%), balance K2O, CaO &
Al2O3
x) Sulphuric Acid Synthesis Catalyst V2O5–(6-8%), CaO-(9-10%), K2O(8-
10%), Cs-(0.5%)*, balance –SiO2, *
for Caseium doped catalyst
ANNEX B (Table 1)
B–1 A TYPICAL ANALYSIS OF ARSENIC SLUDGE
Sl No.
(1)
Composition
(2)
Value %
(3)
i)
ii)
iii)
iv)
v)
As2O3
As2O5
Fe2O3
K2O
Moisture
12.0
11.5
15.5
22.3
38.7
B–2TYPICAL CHARACTERISTICS OF CHROMIUM SLUDGE
B–2.1Physical Characteristics
Nature : Sludge, Slimy, Slightly alkaline
Colour : Light grey
Solubility : Insoluble in water
Odour : Odourless
Combustibility: Non-combustible
B–2.2 Chemical Characteristics
B–3 TYPICAL COMPOSITION OF SULPHUR SLUDGE
Sl No.
(1)
Composition
(2)
Value %
(3)
i) Moisture 1.04
ii) Organic Matter 3.15
iii) Ash 50.11
ix) Sulphur as S 45.7
Sl No.
(1)
Characteristic (%)
(2)
Average Values (%)
(3)
i)
ii)
iii)
iv)
v)
vi)
vii)
viii)
Loss on ignition
Acid insoluble as Silica
Iron as Fe2O3
Chromium as Cr2O3
Calcium as CaO
Magnesium as MgO
Phosphate as P2O5
Zinc as Zn
33.65
16.56
1.49
17.99
18.74
8.50
1.52
1.55
ANNEX C (Table 1)
TYPICAL ANALYSIS OF FLY ASH
ANNEX–D (Table 1)
TYPICAL ANALYSIS OF PHOSPHOGYPSUM(Dihydrate Process)
Sl. No.
(1)
Parameter
(2)
Wt%
(3)
i) Watercryst. 18.0
ii) SO2 43.6
iii) CaO 32.0
iv) MgO 0.40
v) Al2O3+Fe2O3 1.82
v) SiO2 insoluble in HCl 1.64
vi) Na2O 0.36
vii) P2O5total 1.03
viii) Ftotal 0.76
ix) Organic matter 0.26
ANNEX–E (Table 1)
TYPICAL ANALYSIS OF ZINC MUD
Sl. No.
(1)
Parameter
(2)
Wt%
(3)
i) Zn 3-4
ii) Lead as Pb 5-7
iii) Iron as Fe 1-1.5
iv) Aluminum as Al 1-1.5
v) Inert material Balance
Sl No.
(1)
Properties
(2)
Rangc (% w/w)
(3)
i) Combustibles 8.0 to 20.0
ii) SiO2 48.0 to 61.6
iii) Al2O3 15.0 to 20.0
iv) Fe2O3 8.0 to 11.0
v) TiO2 1.3 to 1.7
vi) CaO 0.1 to 0.4
vii) MgO 0.20 to 1.4
viii) Na2O 0.41 to 0.45
ix) K2O 0.61 to 0.80
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