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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

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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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