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RISKASSESSMENT

(QRA)

Proposed Modernization ProjectManufacturing Of Pesticides, Insecticides & Fungicides

At

HIKAL LIMITEDPLOT NO.: A-18 , MIDC MAHAD,

DIST.:- RAIGAD, MAHARASHTRA , INDIA.

MAY 2017

2

CONTENTSSECTION DESCRIPTION PAGE NO.

1. EXECUTIVE SUMMARY. 03

2. HAZARD IDENTIFICATION. 242.1 Site Overview. 242.2 Process Description. 242.3 List Of Materials. 242.4 Inventory Analysis. 242.5 Classification Of Hazardous Chemicals. 242.6 MSDS. (Highlights). 242.7 Mond Index Assessment. 282.8 Dow F & E Index. 402.9 HAZOP Study. 45

3. FAILURE FREQUENCY ANALYSIS.3.1 Failure Frequency. 1343.2 Event Tree Analysis. 135

4. CONSEQUENCE ANALYSIS. 1364.1 Introduction. 1364.2 1 Toxic Hazard – Bromine 137

2 Fire /explosion hazard –Hydrogen 1383 Fire hazard –Toluene 139

5. IMPACT ASSESSMENT (PROBIT). 1475.1 Thermal Radiation Impact. 1475.2 Over Pressure Impact. 1485.3 Toxicity Impact. 149

6. RISK ESTIMATION. 1516.1 Individual Risk Isopleths. 1516.2 Societal Risk (F – N Curve). 152

7 RISK MITIGATION MEASURES. 152

LIST OF ANNEXURESECTION DESCRIPTION PAGE NO.

1. GLOSSARY. 1532. ABBRIVATIONS. 1553. REFERENCES. 156

3

SECTION 1: EXECUTIVE SUMMARY1.1 INTRODUCTION

1.1.1 This report is for the Proposed Modernization Project Manufacturing Of Pesticides,Insecticides & Fungicidesat Plot No.: A-18, MIDC Mahad, District:Mahad,Maharashtra.

1.1.2 The list of products manufactured and production capacity present and proposed areshown in below mix.TABLE NO. 1.1: LIST OF PRODUCTS FOR ENVIRONMENTAL CLEARANCE

Sr. No. ProductExisting(MT/M)

Proposed(MT/M)

Total(MT/M)

1 Ethyclozate 03.00 (-) 01.33 01.672 Amitrol 15.00 (-) 15.00 00.00

35 Methoxy methyl Pyridine 2 , 3Dicarboxyalic acid

50.00 00.00 50.00

4 Diuron 310.00 190.00 500.005 Sodium Hypochloride 480.00 (-) 480.00 00.006 3,5 Dichloroaniline 80.00 70.00 150.00

72 Amino 2 Methyl isopropyloxy6 methyl propiophenone

25.00 (-) 08.33 16.67

84 acetoxy 6 tert butyl 8 floro 2 3dimethyle quinoline

10.00 (-) 01.67 08.33

9 Benefuresate 05.00 05.00 10.0010 Benzophenaf 15.00 00.00 15.0011 Clothianidin 00.00 15.00 15.0012 Trifloxystrobin 00.00 25.00 25.0013 Azoxystrobin 00.00 25.00 25.0014 Thiacloprid 00.00 25.00 25.0015 SMPGM 00.00 15.00 15.0016 Fludioxanil 00.00 25.00 25.00

Total 993.00 (-) 111.33 881.67Formulations 0 84 84

993.00 (-) 27.33 965.67List of By-products:

Sr.No.

By-Product Existing(MT/M)

Proposed(MT/M)

Total(MT/M)

1 *Calcium Sulphate (Gypsum) 212.542 00 212.5422 Sodium Bromide solution 300 300 600.003 Spent Catalyst 0.988 00 0.9884 Hydrochoric Acid (30 %) 50 00 50.005 Acetone 43.5 00 43.506 35% Spent Sulphuric Acid 119.75 00 119.757 10% H2SO4 (3,5 DCA) 102 00 102.008 Potessium bromide 0 172 172.00

Total 828.78 472.00 1300.78

No change New Expansion Scale down Elimination

4

1.2 THE ASSIGNMENT

1.2.1 In compliance to the TOR for synthetic organic chemicals, this QRA report is

prepared.

1.2.2 Mr. Subhash Bonde of M/s. Bonde Technical Services, Thane is “EIA Functional

Expert – Risk Assessment and Hazard Management (RH)” undertook this study in

compliance with requirements of EIA report preparation which is prepared by M/s.

Goldfinch Engineering Systems Private Limited, Thane.

1.2.3 The list of products under each product group is listed in the following table. The

products mix listed here or any similar product of the same group will be within the

specified risk levels.

1.3 SCOPE OF WORK

The scope of the report covers the proposed site activities of manufacturing. The

battery limits of this study are restricted to the installations indicated over the site

plan.

Latitudes 18.104880 N , Longitudes 73.481774 E , Height above MSL20 m

FIGURE 1.1: PROPOSED SITE

5

1.4 METHODOLOGY

Methodology followed in preparation of this report is as per Technical EIA Guidance

Manual for Synthetic Organic Chemicals, prepared for the Ministry of Environment

and Forests Government of India. The major steps are as outlined below;

Hazard Identification.

Failure Frequency Analysis.

Consequence Analysis.

Impact Assessment.

Protective System & Hazard Analysis.

Risk Mitigation Measures.

DMP.

FIGURE NO. 1.2: RISK ASSESSMENT METHODOLOGY.

1.5 HAZARD IDENTIFICATION

1.5.1 INVENTORY ANALYSIS

1.5.1.1 The proposal requires storage and handling of following raw

materials.

6

Table 1.2: PRODUCT WISE RAW MATERIALS ONLY FOR EXISTING PRODUCTSSr.no. Raw material

Eth

yclo

zate

5 M

etho

xym

ethy

lPy

ridi

ne 2

, 3

Dic

arbo

xyal

icac

idD

iuro

n

3,5

Dic

hlor

oani

line 2

Am

ino

2M

ethy

lis

opro

pylo

xy6

met

hyl

prop

ioph

enon

e4 ac

etox

y 6

tert

but

yl 8

flor

o 2

3di

met

hyle

quin

olin

eB

enef

ures

ate

Ben

zoph

enaf

1 2,6 DCPNA √2 3,5 DCNB √3 Bromine* √4 DMA* √5 DME √6 Sodium Azide* √7 THF* √8 TMA √9 Xylene* √10 Melonic acid √11 Ammonium formate √12 CNBA √13 Sodium bi carbonate √ √ √14 Catalyst √ √15 Sodium nitrite √16 3,4 DCPI √17 PRO √18 CPP √19 TBAB √20 TBU √21 Diphenyl ether √22 EMM √23 PA √24 MY 710 √25 PMPC √Table 1.2: PRODUCT WISE RAW MATERIALS COMMON FOR FOR EXISTING PRODUCTSAND NEW PRODUCTSSr.no. Raw material

Eth

yclo

zate

5 M

etho

xym

ethy

l Pyr

idin

e2

, 3D

icar

boxy

alic

acid

Diu

ron

3,5

Dic

hlor

oani

line

2 A

min

o 2

Met

hyl

isop

ropy

loxy

6m

ethy

lpr

opio

phen

one

4 ac

etox

y 6

tert

buty

l 8 f

loro

2 3

dim

ethy

lequ

inol

ine

Ben

efur

esat

e

Ben

zoph

enaf

Clo

thia

nidi

n

Tri

flox

ystr

obi

nA

zoxy

stro

bin T

hiac

lopr

id

SMPG

M

Flud

ioxa

nil

1 Act. Carbon √ √2 Ethanol * √ √3 Ethylene

Dichloride.*√

4 Formic acid * √ √5 Hydrazine hydrate √6 Hydrochloric acid * √ √ √ √7 Hydrogen* √ √8 Iso propyl alcohol * √9 Methanol* √ √ √ √ √ √ √ √ √10 MIBK * √ √11 N hexane* √12 Sodium boro hydride √13 Sodium hydroxide* √ √ √ √ √ √14 Sulfuric acid* √ √ √ √ √ √15 Toluene* √ √ √ √ √ √16 Tri ethyl amine * √ √ √

7

Table 1.2: PRODUCT WISE RAW MATERIALS ONLY FOR NEW PRODUCTS

Sr.no.

Raw material

Clo

thia

nidi

n

Tri

flox

ystr

obin

Azo

xyst

robi

n

Thi

aclo

prid

SM

PG

M

Flu

diox

anil

1 1,2 di methoxy ethane √2 Acetic anhydride* √3 Acetophonone √4 Di ethyl ether √5 DMF √6 Ethyl acetate * √7 Ethyl cyano acetate √8 Formaldehyde 37 √9 KHF2 √10 MCB * √11 MMA* √12 N butyl lithium √13 Nitramide √14 Phosphrous oxy chloride * √15 Phosphrous penta chloride * √16 Potassium fluride √17 Sodium cyanide* √18 Sodium p – toluene sulfonate √19 Tetramethyl sulfone √20 Methoxyiminoacetic acid methyl ester ( 2 bromomethyl

phenyl )√

21 Potassium carbonate √ √22 Ethanone oxime (1-(3-trifluromethyl phenyl ) √23 Ethyl -2(2-(6 chloropyrimidine -4yloxy)phenyl -3-

methoxyacrelate√

24 1,4 diazobicyclo (2,2,2) octane √25 2-cyano phenol √26 Cysteamine hydrochloride 72% √27 CDIM √28 CCMP √29 Sodium carbonate √ √30 Ammonium carbonate √31 Alpha MBA √32 Triethyl orthoformate √33 Benzo (1,3) dioxole √

* listed in schedule I of part II of MSIHC rules 1989.Raw materials for proposed elimination Products Amitrol and Sodium Hypochlorideare not considered .

8

1.5.1.2 HAZARDOUS CHEMICALS

Chemicals stored or handled at site are Hazardous chemicals which satisfies; any of thefollowing criteria.1. Criteria laid down in part I or is listed in Column 2 of Part II Schedule I appended to

“Manufacture Storage and Import of Hazardous Chemicals Rules, 1989” and2. Criteria laid down in part I or is listed in Column 2 of Part II Schedule I appended to

“The Maharashtra Factories (Control of Industrial Major Accident Hazards) Rules,2003” or

3. Listed in Column 2 of Schedule 2 appended to these rules or4. Listed in Column 2 of “The Second Schedule appended to the Factories Act, 1948”.5. “The Hazardous Waste (Management and Handling) Rules, 1989” Amended 2000

and 2003.

1.5.1.3 PROPERTIESProperties Part I

Sr.No. NAME CAS LEL UEL F.P B.P. *

Nf

*Nr

MF

% % 0c 0c1 Sodium cyanide 143-33-9 - - - 1496 0 0 12 Bromine. 7726-95-6 - - - 58 0 0 13 Ammonia (Anh). 7664-41-7 16 25 11 -33.34 1 0 44 Ammonia liquor 1336-21-6 - - 1 0 45 Formic acid 64-18-6 18 51 69 101 2 0 106 Diesel 68476-34-6 0.6 7.5 32 -62 >150 2 0 107 Di methyl formamide 68-12-2 2.2 15.2 58 2 0 108 Furnace oil HC Mix 0.7 5 >65 175-325 2 0 109 Sodium hydroxide 1310-73-2 - - - 1390 0 1 1410 Acetic anhydride 108-24-7 2.7 10.3 49 139 2 1 1411 Hydrochloric acid 7647-01-0 - - - 53 0 1 1412 Hexane 110-54-3 1.2 7.7 -23 55 3 0 1613 Tri ethyl amine 121-44-8 1.2 8 -17 89 3 0 1614 Acetone 67-64-1 2.2 13 -18 56 3 0 1615 THF 109-99-9 2 11.8 -14.5 66 3 0 1616 Ethyl Acetate 141-78-6 2 11.5 -4 77 3 0 1617 Methanol. 67-56-1 6 36 11 64.7 3 0 1618 Iso propyl alcohol 67-63-0 2 12.7 12 82 3 0 1619 Toluene 108-88-3 1.2 7 12.7 110.4 3 0 1620 Ethanol 64-17-5 3.3 19 13 79 3 0 1621 Ethylene Dichloride. 107-06-2 6.2 15.9 13 83.4 3 0 1622 MIBK 108-10-1 1.4 7.5 14 117-118 3 0 1623 Mono Chloro Benzene 108-90-7 1.3 11 27 132 3 0 1624 Xylene 1330-20-7 1 7 32 144 3 0 1625 DMA soln 124-40-3 2.8 14.4 -18 51 4 0 2126 Tri Methyl amine 40 % 75-50-3 2 16.6 -7 30 4 0 2127 Tri Methyl amine 75-50-3 2 16.6 Gas 3 4 0 2128 Hydrogen 1333-74-0 4 76 Gas - 4 0 2129 Mono methyl amine 74-89-5 4.9 20.7 gas -6 4 0 2130 Phosphrous penta chloride 10026-13-8 - - - 100** 0 2 2431 Sodium boro hydride 16940-66-2 - - - 1 2 2432 Sodium Azide 26628-22-8 - - - *** 0 2 2433 Sulphuric acid 7664-93-9 - - - 290 0 2 2434 Phosphorous Oxychloride* * 10025-87-3 - - - 105.8 0 2 24* NFPA HAZARD INDEX Nf –flammability ; Nr –reactivity** sublimes***Decomposes ;MF =material factor

9

Properties Part II

Sr.No.

NAME CAS Nh TLV STEL IDLHorallD50

dermallD50

InhalationLC50

Ppm ppm Ppm Mg/kg ml/kg Ppm

1 Thinoyl Chloride 9/7/7719 4 1 ppm C#

2 Bromine. 7726-95-6 4 2 mg/m3 C# 2600 2700mg/m3

3 Sodium boro hydride 16940-66-2 3

4 PhosphorousOxychloride 10025-87-3 3 0.1

5 Phosphrous penta chloride 10026-13-8 3 0.1

6 Sulphuric acid 7664-93-9 3 1 mg/m3 100-330 mg/m3

7 Tri Ethyl amine 121-44-8 3 1 3

8 Sodium hydroxide 1310-73-2 3 2 mg/m3 - 50 ug -

9 Tri Methyl amine 75-50-3 3 5

10 Acetic unhydride 108-24-7 3 5 1.78 4ml/kg 1000

11 Hydrochloric acid 7647-01-0 3 5 50 3124 900

12 Mono Methyl amine 74-89-5 3 5 15

13 Tri Ethyl amine 75-50-3 3 5 15

14 Sodium cyanide 143-33-9 3 5 mg/m3

15 Formic acid 64-18-6 3 5 10

16 Formic acid 64-18-6 3 5 15

17 Ammonia liquor 1336-21-6 3 25 0.35 250ug -

18 Ethylene Dichloride. 107-06-2 2 10 670 2800 1000

19 Mono Chloro Benzene 108-90-7 2 10

20 Di methyl formamide 68-12-2 2 10 PEL 2800 4720

21 Ammonia (Anh). 7664-41-7 2 25 35 500 350 4000

22 Toluene 108-88-3 2 50 150

23 MIBK 108-10-1 2 50 75

24 Xylene 1330-20-7 2 100 150 4300 >1700 5000

25 THF 109-99-9 2 200

26 Iso propyl alcohol 67-63-0 2 400 100 mg/l.

27 Hexane 110-54-3 1 50

28 Furnace oil HC Mix 1 200 >500

29 Methanol. 67-56-1 1 200 250 5.628 15.8g/kg 64000 ppm

30 Ethyl Acetate 141-78-6 1 400 -- 2000 5.62 >20ml/kg 200g/m3

31 Acetone 67-64-1 1 750 750 5800

32 Hydrogen 1333-74-0 0 asphyxiant SA - SA

33 Diesel 68476-34-6 0 5 10-15 - 7.5 - -

34 Ethanol 64-17-5 0 1000

35 Sodium Azide 26628-22-8 0.290.11as HN3

36 Clothianidin 210880-92-5 NA >5000 >2000 > 5538 mg/m3

37 Trifloxystrobin 141517-21-7 2.7 mg/m3TWA

>2.000 >2.000 NA

38 Azoxystrobin 131860-33-8 NA NA NA NA

39 Thiacloprid 40.4 %Glycerine 10%

111988-49-956-81-5

10 mg/m3 TWA >300-<500

>4000 >1.0-<2.2 mg/l

40 SMPGM 5933-41-5 NA NA NA NA41 Fludioxanil 131341-86-1 NA >5050 >2020 >3.77 mg/l

*NFPA HAZARD INDEX Nh –Health

C# - Ceiling

1.5.1.4 MSDS

MSDS of Bromine , Hydrogen and Toluene are enclosed in Section No. 2 and MSDS

for finished goods , others raw materials are maintained at site.

10

1.5.1.5 INVENTORYTable 1.4 INVENTORY

Sr.no

Name Max quantity stored Mode of storage Location

Existing Addition Final1 2,6 DCPNA 6 MT 6 MT 500 kg Jumbo Bags FG/RM Store (52)

2 Acetic unhydride -- 1.0MT 1.0MT Drums FG/RM Store (52)3 AIBN 0.40 0.40 20 kg Drum FG/RM Store (52)4 Ammonia 1.0 T 1.0 T Tank Cylinders for utility

perpose only5 Bromine 20 KL 20 KL 10 KL 2 Tank tank farm (70)6 DCPI 70 KL 70 KL 50 kl & 30 KL Tank Separate tank farm7 Diesel 0.2 kl 0.2 kl Drum DG room8 Ethyl Acetate 20 MT 20 MT 30 KL Tank Class A/B /C tank

farm (X4)9 Ethylene Dichloride. 30 KL 30 KL 30 KL Tank tank farm (68)10 Hydrochloric acid 15 MT 15 MT 20 KL Tank Acid tank farm11 Hydrogen 0.25 0.25 1 Trolley X2 hydrogen shed

(23)12 Iso propyl alcohol 20 KL 20 KL 20 KL Tank Class A/B /C tank

farm (X4)13 Methanol 20 KL 20 KL 20 KL Tank Class A/B /C tank

farm (X4)14 MMA -- 2.0MT 2.0MT drums FG/RM Store (52)15 MTCA 06 MT 06 MT 20 kg Cartoon/

corrugated BoxFG/RM Store (52)

16 N-N, Dimethylfarmamide)

-- 02 MT 200 kg Drums FG/RM Store (52)

17 Pd Catalyst 0.5 MT -- 0.5 MT 50 kg Carboy FG/RM Store (52)18 Sodium Azide 2.0 MT 2.0 MT 200 kg Drum Hazardous storage

shed (71)19 Sodium nitrite 4 MT 4 MT 50 kg Poly bags FG/RM Store (52)20 Sulfuric acid 19 KL 19 KL 19 KL Tank Acid tank farm ( 32)21 Tetra Hydro Furan 55 KL 55 KL 30 KL 2 Tank Class A/B /C tank

farm (X4)22 Thionyl Chloride 02MT 02MT 200 kg Drums FG/RM Store23 TMA 5.535 5.535 5.0 KL Tank tank farm X324 Toluene 30 KL 30 KL 30 KL Tank Class A/B /C tank

farm (X4)25 Furnace oil 20 KL 20 KL Tank X4( figure in bract indicates the installation location block number on the master site plan )

Finished productsSr.no

Name Max qtystored

Mode of storage Locationblock no. onsite plan

1 Ethyclozate 2 MT 50 kg 40 Bags 522 Amitrol 2 MT 50 kg 40 Bags 523 5 Methoxy methyl Pyridine 2 , 3 Dicarboxyalic acid 30 MT 50 kg 600 Bags 524 Diuron 50 MT 50 kg 1000 Bags 525 3,5 Dichloroaniline 40 MT 40 KL Tank 696 4 acetoxy 6 tert butyl 8 floro 2 3 di methyl equino line

4 MT50 kg 80Bags/cartoons

52

7 Benefuresate 2 MT 2kl 528 Benzophenaf 2 MT 50 kg 40 Bags 52

11

Bi productsSr.no

Name Max qtystored

Mode of storage Location block no.on site plan

1 *Calcium Sulphate (Gypsum) 40 MT Shed 582 Sodium Bromide solution 40 MT 40 KL Tank 683 Spent Catalyst 1 MT 200 kg 5 Drums Left side of 724 Hydrochoric Acid (30%) 20 MT 30 KL Tank 325 Acetone 10 MT 20 KL 2 Tank 576 35% Spent Sulphuric Acid 10 MT 20 KL Tank 327 10% H2SO4 (3,5 DCA) 10 MT 10 KL Tank 32

1.5. CLASSIFICATION OF HAZARDOUS CHEMICALS

TABLE NO. 1.5: HAZARDOUS CHEMICALS CLASSIFICATION

Sr.No. Group Material Max.Storage

Capacity

ThresholdQty. Mt.for MAH

(Sch. 2)*

Group 2 : Toxicchemicals

Bromine 86 40

1 Group 3 : Highlyreactive chemicals

Hydrogen 0.25 2

2 Group 5.3 : Very HighlyFlammable Liquids.

Chemicals having flash point ≤23 0 C & boiling point < 35 0 C

Less thanthreshold

1500 T.

3 Group 5.5 : HighlyFlammable Liquids.

Chemicals having23 0 C < flash point ≤ 60 0 C

Less thanthreshold

2500 T

4 Group 5.6: FlammableLiquids.

Chemicals having60 0 C < flash point < 90 0 C

Less thanthreshold

5000 T

*Criteria used: “Manufacture Storage and Import of Hazardous Chemicals Rules,1989”.

1.6 DOW FIRE , EXPLOSION & TOXICITY INDEX

Identification of hazardous units and segments of plants and storage units based on

“relative ranking technique,” such as Fire and Explosion Index. F & EI, is a method

universally adopted for classifying/ categorizing/ indexing of chemicals based on their

reactivity and instability. The more widely used hazard index is the F & EI developed

by DOW Chemical Company. Dow Fire and Explosion Index (F&EI) serve as a guide

to the selection of fire protection methods. Methodology adopted is described in

Section No. 2.8.

12

TABLE NO. 1.6: DOW INDEX

Sr.

No.

Installation DOW

F&E

Index

The

Degree Of

Hazard

Radius Of

Exposure

(m)

Damage

Factor

Toxicity

Index

Toxicity

Category

1 Bromine 3.2 Light 0.81 0.04 8.25 II

4 Hydrogen 59 Light 15 0.58 - -

3 Toluene 38 Light 9.7 0.35 4.4 I

1.7 MOND INDEX ASSESSMENT

1.7.1 The MOND Index is a rapid hazard assessment method for use on chemical

plant or in plant design. The use of this technique puts the hazard of a plant on

a numerical scale, where the comparative pictures of all subdivisions of the

plant form emerge. The assessment is carried out as per MOND INDEX

Manual 1993. Methodology adopted is described in Section No. 2.7.

TABLE NO. 1.7: MOND INDEX ASSESSMENT

SR. O. MATERIAL OVER ALL HAZARD RATING

1 Bromine 11 Mild

2 Hydrogen 391 Moderate3 Toluene 434 Moderate

1.7.2 It is reasonable to assume that a unit assessed at this level can be operated in a

satisfactory manner by providing adequate off setting measures, giving full

regard to the hazards indicated by the assessment provided adequate depends

heavily upon the maintenance of the hardware and of the management

procedures; neglect of either will lead to loss of protection and the rating will

rise.

13

1.8 COMPATIBILITY/ REACTIVITY HAZARD

TABLE NO. 1.8: COMPATABILITY /REACTIVITY HAZARD MATRIX

Chemicals Mixing With →

Ace

tic

Anh

ydri

de

Hyd

roch

lori

c A

cid

Isop

ropa

nol

N,N

-D

imet

hylf

orm

amid

e

Sod

ium

Azi

de

Tri

ethy

lam

ine

1 Acetic Anhydride2 Hydrochloric Acid N3 Isopropanol C C4 N,N-Dimethylformamide Y N Y5 Sodium Azide C N C Y6 Triethylamine N N Y C N

CHART LEGEND

Y Compatible - No hazardous reactivity issues expected

N Incompatible - Hazardous reactivity issues expected

C Caution - May be hazardous under certain conditions

SR Self reactive - Potentially self reactive e.g. polymerizable

1.9 HAZOP STUDY(Enclosed separately).

1.9.1 Identification of hazards by HAZOP study is carried out, the thrust area being

the environmental issues in the proposed activities. The report is “Enclosed

separately”. The methodology adopted is described in the report.

1.9.2 HAZOP COMMITTEE

HAZOP committee was formed under the chairmanship of Project proponent

with members of the project team and Mr. Subhash Bonde as Moderator.

14

1.9.3 UNIT PROCESS AND UNIT OPERATIONS

Table no. 1.9:product wise unit processes &operations

Sr.No.

UnitProcesses/Operations

Product number in which the corresponding process/operation isused.

Eth

yclo

zate

5 M

etho

xy m

ethy

l Pyr

idin

e 2

, 3 D

icar

boxy

alic

aci

d

Diu

ron

3,5

Dic

hlor

oani

line

2 A

min

o 2

Met

hyl

isop

ropy

loxy

6 m

ethy

l pro

piop

heno

ne

4 ac

etox

y 6

tert

but

yl 8

flo

ro 2

3 d

imet

hyle

qui

nolin

e

Ben

efur

esat

e

Ben

zoph

enaf

Clo

thia

nidi

n

Tri

flox

ystr

obin

Azo

xyst

robi

n

Thi

aclo

prid

SM

PG

M

Flu

diox

anil

1Charcoaltreatment

√

2 Crystallization √ √3 Deamination √4 Dehydration √ √ √5 Distillation √ √ √ √ √ √ √ √ √ √ √6 Drying √ √ √ √ √ √ √ √ √ √7 Esterification √8 Extraction √ √ √ √ √ √9 Filtration √ √ √ √ √ √ v √ √ √ √10 Halogenation √ √11 Hydrogenation √12 Hydrolysis √ √13 Methoxylation √14 Quarternization √15 Washing √ √ √Reaction Exotherm.

Critical To Control Moderate Mild

1.9.4 NODES

The HAZOP Study carried out under following NODES;

15

TABLE NO. 1.10: NODES FOR HAZOP STUDY

Node 1 Tank farm.Node 2 H alogenation

Sub node 2.1 : Bromine storage and handlingSub node 2.2 : Process operations

Node 3 HydrogenationSub node 3.1 : Hydrogen cylinder trolley handlingSub node 3.2 : Hydrogenation product process operations

Node 4 EsterificationNode 5 HydrolysisNode 6 Other unit processes and operationsNode 7 Effluent treatment plant.

.9.5 MODES Batch Wise Mode.

1.9.6 IDENTIFICATION OF HAZARDS1.9.6.1 HAZARD RATING

Probability of each hazard according to its likelihood ofoccurrence and the severity of each hazard according to itspotential for harm was estimated on 1 to 5 scale. Bymultiplying these two factors i.e. probability and severity, arange of risk ratings between 1 to 25 is obtained.

1.9.6.2 Identified hazards/ events having risk rating in 16 to 25 rangesummarized as follows;

STORAGE AND HANDLING Fire/ explosion hazard at tank farm. Reactivity/ compatibility hazards due to large number of

chemicals.

PROCESS OPERATIONS Fire/ Explosion hazard at reactor due to uncontrolled

exothermic reactions. Health hazard due to vapors emissions at work place. Fire explosion hazard due to Static charge as source of

ignition in handling of solvents. Toxic gas release at scrubber vent

1.9.6.3 Following accident scenario is considered for ConsequenceAnalysis. Release of Bromine Release of Hydrogen followed by Fire/explosion Spill of Toluene followed by pool fire.

16

1.10 CONSEQUENCE ANALYSIS1.10.1 The potential consequences from the hazardous scenarios identified are

determined and the impact zones modeled using ALOHA and PHASTsoftware tools. The primary consequence types are pressure wave, thermalradiations and toxic gas release. The neutral atmospheric stability conditionsand ambient temperature of 30 oC, wind speed was 4.0 m/s. and humidity(50%) used for Consequence Analysis.

1.10.2 RESULTSTABLE NO. 1.11: CONSEQUENCE ANALYSIS RESULTS

Sr. Downwind Affect Distance (m)

No.Accident Scenario Toxic vapor cloud

Flammablevapor cloudLEL

ERPG 3 ERPG 2 ERPG 1 IDLH 60 % 10 %1 Bromine release 803 3400 8000 1100 NA NA2 Hydrogen release NA NA NA NA 30 733 Toluene release <10 <10 <10 <10 <10 <10

Sr. Downwind Affect Distance (m)

No.Accident Scenario Blast Over Pressure psi Thermal radiation (KW/m2)

8 3.5 1.0 10 5 21 Bromine NA NA NA 14 17 232 Hydrogen release 24 27 45 18 25 382A Hydrogen Jet fire NA NA NA <10 <10 <103 Toluene pool fire NA NA NA 10 13 17

FIGURE 1.3: CONSEQUENCE COUNTER MAPDISPERSION EXPLOSION. Hydrogen cloud side view

BROMINE HYDROGEN HYDROGEN

17

1.11 FREQUENCY ASSESSMENT

1.11.1 Event trees begin with an initiating event and work toward a final result. Thisapproach is inductive. The method provides information on how a failure canoccur and the probability of occurrence.

1.11.2 EVENT TREEFrequency of the incident is estimated by Event Tree.

TABLE 1.12 : EVENT FAILURE FREQUENCY

S.N. EVENT EVENT FREQUENCY/YR

1. Hydrogen gas accidental fire/explosion. 4.4 X 10-3

2. Bromine release from evaporating pool 1.9 10-3

3 Release of flammable solvent followed by pool fire. 1.0 10-4

1.12 IMPACT ASSESSMENT

1.12.1 Effect models are used to determine how people are injured by exposure toheat, overpressure and toxic load. Effect models make use of a probit function.In probit function a link exists between the load and percentage of peopleexposed who suffer particular type of injury.

TABLE NO. 1.13: PROBIT CORRELATION RESULTS

Level OfConcern

AffectDistance Impact Probit Correlation Fatality

*Event-release of Toluene

8.7 KW/m2 <10 Thermal Radiations. Pr = –14.9+ 2.56 ln [(t×I4/3)] 109.7 KW/m2 <10 Thermal Radiations. Pr = –14.9+ 2.56 ln [(t×I4/3)] 20

Event-release ofOver pres. 3.5 psi 27 m Lung Hemorrhage. Pr = –77 + 6.91 ln (Po) 54 %Over pres. 3.5 psi 27 m Ear Drum Rupture. Pr = –15.6 + 1.93 ln (Po) 5%Over pres. 3.5 psi 27 m Fatality. Pr = –46.1 + 4.82 ln (Po) 010.0 KW/m2 18 m Thermal radiations. Pr = –14.9+ 2.56 ln [(t×I4/3)] 0

Event-release of Bromine2311 ppm Conc. 54 m Toxicity. Pr = –9.04 + 0.92 [ln (C2.0×T)] 99680 ppm Conc. 102 m Toxicity. Pr = –9.04 + 0.92 [ln (C2.0×T)] 50324 ppm Conc. 149 m Toxicity. Pr = –9.04 + 0.92 [ln (C2.0×T)] 10183 ppm Conc. 213 m Toxicity. Pr = –9.04 + 0.92 [ln (C2.0×T)] 1

* Assuming escape time from fire to safe place less than 81 seconds.

18

1.13 RISK ESTIMATION

1.13.1 VULNERABLE ZONE

FIGURE 1.4: VULNERABLE ZONE.

ContourNo.

Chemical Level Of Concern Impact

1 Hydrogen. 3.5 psi over pressure Overpressure wave

19

2 Hydrogen. Dow damage radius Damage factor 0.583 Bromine ( line leak ) ERPG 3 concentration Toxicity4 Bromine (Tank failure) ERPG 3 concentration Toxicity5 Toluene Dow damage radius Damage factor 0.35

1.13.2 INDIVIDUAL RISK

Average individual risk (exposed hours/worked hours)

( Manpower at site skilled 66 nos, semiskilled 55 nos unskilled 14 nos. and

casual 30 nos . )Individual risk to personnel at Assembly point

INDIVIDUAL RISK (IR) = (1 /N ) ∑ Ii x fi

whereN = number of persons ( 165 nos. )i Incident identification numberI, = impact of Incident ifi = frequency of the i incident

S.N. ReleaseIncident

I

IncidentFrequency

/ Yr

Impact at AP Level OfConcern

Level OfConcernAt AP

Fatality

1 Hydrogen 4.4 X 10-3 Lung Hemorrhage. 3.5 psi Not reached 54 %2 4.4 X 10-3 Ear Drum Rupture. 3.5 psi Not reached 5%3 4.4 X 10-3 Fatality. 3.5 psi Not reached 0

Bromine 1.9 10-3 Toxicity ERPG 3conc.

57.9 ppm outdoor18.6 ppm indoor

0

4 Toluene 1.0 10-4 Thermal radiations. 10 Kw /m2 Not reached 27%

Individual risk at assembly point

1.13.3 INDIVIDUAL FATALITY CRITERIA

Table 1.14 : INDIVIDUAL FATALITY CRITERIA

Individual Fatality (IR) Individual Fatality Criteria

1 × 10-4 per year This contour remains on-site.

1 × 10-5 per year This contour extends into industrial developments only.

1 × 10-6 per year This contour extends into commercial and industrial developmentsonly.

1.13.4 QRA RESULTS

Table 1.15 : INDIVIDUAL RISK RESULTS

Contour No. Individual Fatality (IR)Downwind

Affect Distance(M)

Remarks

1. 1 × 10-4 per year. 54 This contour extends outside the site2. 1 × 10-5 per year. 149 This contour extends into industrial

20

developments3. 1 × 10-6 per year. 213 This contour extends into industrial

developments

1.13.5 SITE SURROUNDING: MIDC AREA

Figure 1.5: MIDC AREA.

1.13.6 SITE SURROUNDING

Figure 1.6 : SITE SURROUNDING POPULATION

21

1.13.7 SOCIETAL RISK

TABLE 1.16 : QRA RESULTS.

QRA RESULTS. F – N CURVE.

R.NO.

RELEASE EVENTEVENT

FREQUENCYPER YR

NO. OFFATALITY

CUMULATIVEFREQUENCY

1. Bromine 1.9 10-3 2 1.9 10-3

2 Hydrogen 4.4 10-3 1 6.3 10-3

3 Solvent 1.0 10-4 0 6.4 10-3

1.14 RISK MITIGATION MEASURES SUGGESTED

1. Fire hydrant system .

2 . Bromine storage and handling

a) Minimize the dispersal of bromine vapors by locating the storage area on lowground. Low curbs or walls (called dikes). 200 mm high, should enclose thestorage area to protect the area from external flooding and to minimize thedispersal of bromine vapors. The minimum diked volume should be equivalentto the largest storage tank plus 10%.

b) The diked area should not have a sewer connection. Provide an adequate sizesump for collecting bromine spills and pump away collected rainwater andfire-fighting water. Fire-fighting water should be prevented fromcontaminating water sources.

c) Bromine handling area Floors should be of impervious construction,preferably concrete.

d) There should be a strengthened approach way for emergency vehicles on twosides of the installation.

e) Neutralization dry Bromates (products of Sodium Hydroxide neutralization ofBromine generated during bromine spill handling operations ) are powerfuloxidants and are shock sensitive. They need to be handled with extreme carewhile disposal .

f) Provide leak detectors at strategic locations at storage as well as consumptionpoint and scrubber vent with signal at control room and ECC

g) Electrical installation:

22

h) Junction boxes and light fittings should be dust and vapor tight.

Do not use aluminum or aluminum alloys unless suitably coated. Use Totally Enclosed Fan Cooled (TEFC) motors of cast iron or steel

construction and epoxy-based coating.

i) A wind sock should be clearly visible from all points on the site and replacedas required. This is required for indicating wind strength and direction.

j) There should be sufficient bromine storage tank capacity or an empty isotankto accommodate the transfer of bromine from a leaking container.

k) Emergency respirator equipment cabinets should be installed not more than 30meters or ten seconds walking distance from any location in the storage area.

l) Signs should be posted prominently at the site entrance and throughout theinstallation with area maps showing access ways, hydrant locations,emergency showers, location of emergency equipment and emergencytelephone numbers.

3. Provide Hydrogen gas leak detectors and alarm at Hydrogen trolley locationand hydrogenation plant.

4. Store chemicals considering the compatibility and reactivity hazards at store/warehouse.

5. Ensure complete distruction of sodium cyanide in the effluent stream beforemixing it to any other stream .

6. Chlorine is not used in the proposed product mix hence Eliminate anyresidual stock of chlorine (if any )at site .

7. Methyl mercaptan is generated in Thiacloprid process . being a odor neusenceany release of the gas should be sent to incineration followed by effectivescrubbers .

8. Provide suitable arrangement in drain system to avoid any organiccontaminated water generated during accidental spill ,floor washings ,sprinkler water , fire fighting water water entering in storm darin system .

9. Revise “DMP” based on MCLS Analysis for the site with dove tailing data foroffsite disaster control plan.

23

FIGURE 1.7 : SITE PLAN AFTER RISK ASSESSMENT

24

1.16 We thank the staff and the management for positive approach shown and excellent co-

operation extended throughout the studies to complete the studies in scheduled time

frame.

25

SECTION 2: HAZARD IDENTIFICATION

2.1 SITE OVERVIEW

2.1.1 M/S. Xxx Oil ltd. is proposing to set up OrganicManufacturing unit at Plot

No. B -14 MIDC Industrial Area ,Mahad , Taluka Mahad , District Raigad

Maharashtra.

2.1.2 Proposed product mix capacity for environmental clearance

Refer Table No. 1.1 in Section No. 1.2.1.2 LIST OF PRODUCTS FOR ENVIRONMENTAL CLEARANCE

Refer Table No. 1.1 in Section No. 1.

2.2 PROCESS DESCRIPTION

Refer HAZOP Study report for process, flow chart, material balance and plant

equipment details.

2.3 LIST OF MATERIALS

2.3.1 FINISHED PRODUCTSRefer Table No. 1.1 in Section No. 1.

2.3.2 RAW MATERIALSRefer Table No. 1.2 in Section No. 1.

2.4 INVENTORY ANALYSISHAZARDOUS CHEMICALS

Chemicals stored or handled at site are Hazardous chemicals which satisfies; any of

the following criteria.

1. Criteria laid down in part I or is listed in Column 2 of Part II Schedule I appended to“Manufacture Storage and Import of Hazardous Chemicals Rules, 1989” and

2. Criteria laid down in part I or is listed in Column 2 of Part II Schedule I appended to “TheMaharashtra Factories (Control of Industrial Major Accident Hazards) Rules, 2003” or

3. Listed in Column 2 of Schedule 2 appended to these rules OR4. Listed in Column 2 of “The Second Schedule appended to the Factories Act, 1948”.5. “The Hazardous Waste (Management and Handling) Rules, 1989” Amended 2000 and 2003.Properties of the chemicals are checked to classify the hazardous chemicals.Refer Table No. 1.3 in Section No. 1.

2.5 CLASSIFICATION OF HAZARDOUS CHEMICALS

Refer Table No. 1.5 in Section No. 1.

26

2.6 MSDS

29

2.7 MOND INDEX ASSESSMENT

2.7.1 METHODOLOGY

The MOND Index is a rapid hazard

assessment method for use on

chemical plant or in plant design.

The use of this technique puts the

hazard of a plant on a numerical

scale, where form the comparative

pictures of all subdivisions of the

plant emerges. (For details refer

MOND INDEX Manual 1993). The

plant installations having significant

inventory of flammable/

combustible materials are

considered and plant is sub divided

accordingly. MOND INDEX

ASSESSMENT (without offsetting) for

these installations is summerised.FIGURE NO. 2.1:

THE MOND INDEX PROCEDURE.

FIRE INDEX (F):

The Index concentrates on the amount of flammable material in the unit, its energyrelease potential and the area of the unit. The expression is;

N

KBF

And descriptive categories can be derived from the table below.TABLE NO. 2.4: FIRE INDEX CATEGORY.

FIRE INDEX CATEGORY0 – 2 Light.2 – 5 Low.5 – 10 Moderate.10 – 20 High.20 – 50 Very High.50 – 100 Intensive.100 – 250 Extreme.> 250 Very Extreme.

30

EXPLOSION INDICES (E):

Separate indices have been developed to indicate the potential of the unit for an

internal explosion an aerial (vapor cloud) explosion.

Internal Explosion Index (E) this is expressed as follows,

1001

SPME

And gives a measure of the potential for explosion within the unit. Corresponding

descriptive categories are given below.

TABLE NO. 2.5: INTERNAL EXPLOSION INDEX CATEGORY.

INTERNAL EXPLOSION INDEX CATEGORY0.0 – 1.5 Light.1.5 – 2.5 Low.2.5 – 4.0 Moderate.4.0 – 6.0 High.Above 6.0 Very High.

AERIAL EXPLOSION INDEX (A):

Important features in assessing aerial explosion risk include the quantity of material

available and its heat of combustion, the likelihood of release, the rate and height of

release and the mixing characteristics of the gas. All of these factors have been

considered to give an aerial explosion index according to the expression. Where, B is

material factor, characteristic of the material.

ptQHEm

BA

1

300

273

10001001

Corresponding descriptive categories are given below;

TABLE NO. 2.6: AERIAL EXPLOSION INDEX CATEGORY.

AERIAL EXPLOSION INDEX CATEGORY0 – 10 Light.10 – 30 Low.30 – 100 Moderate.100 – 400 High.400 – 1700 Very High.Above 1700 Extreme.

31

OVERALL HAZARD RATING (R):

As it is often necessary to compare units having different types of hazard, an overall

hazard index has been developed based upon the indices described above. The

combination adopted is, with the descriptive categories as given below.

AFEDR 2.01

TABLE NO. 2.7: OVERALL HAZARD RATING CATEGORY.

OVERALL HAZARD RATING CATEGORY0 – 20 Mild.

20 – 100 Low.100 – 500 Moderate.500 – 1100 High (Group 1).1100 – 2500 High (Group 2).

2500 – 12,500 Very High.12500 – 65,000 Extreme.Above 65,000 Very Extreme.

EQUIVALENT DOW INDEX:

1001

1001

1001

TLQSPMBD

2.7.2 SUB – DIVISION OF PLANT IN UNITS

Storage tank installations.

41

2.8 DOW F & E INDEXHAZARDS IDENTIFICATION BY USE OF DOW INDEX:

By Dow's Fire and Explosion Index Method:

Fire and Explosion Index, F & EI, is a method universally adopted for classifying/

categorizing/ indexing of chemicals based on their reactivity and instability. The more

widely used hazard index is the F & EI developed by DOW Chemical Company.

1. Identification of equipment within a process plant that would contribute to the

initiation or escalation of an incident.

2. Qualification of the expected damage potential of fire and explosion incident

in realistic terms.

3. Determination of area of exposure surrounding the process unit.

The quantitative methodology relies on the analysis based on historical loss

data, the energy potential of the material under study and the extent to which

loss prevention measures are already taken.

F & EI = MF F3

Where,MF = Material factor which represents in flammability and Reactivity of substance.F3 = Hazard Factor.

= F1 × F 2

Where,F1 = Process Hazard.F2 = Special Process Hazard.

Deviation of MF

MF is a measure of intrinsic rate of potential energy release from fire or explosion

produced by combustion or any other chemical reaction. The National Fire Protection

Agency of U.S.A. (N.F.P.A.) has specified standard values of MF for many

substances. It is calculated from Flammability (Nf) and Reactivity (Nr) indices

provided in NFPA 325 M or NFPA-49. Knowing Flash Point (FP) and Boiling (B.P.)

Flammability can be determined.

General Process Hazard (F1)

42

Six operations, process units or processing conditions which contributes to a

significant enhancement of potential for fire and explosion have been identified and

numerical values of penalties to be added for obtaining the values of F1 are given.

These includes exothermicity and endothermicity of reactions, method of handling,

accessibility and facilities to drainage and spill control.

Special Process Hazards (F2) are factors that contribute primarily to the probability of

occurrence of a loss accident.

Evaluation of F & EI

The degree of hazard potential is identified based on the numerical value of F & E as

per the criteria given below:

TABLE NO. 2.8: F&EI RANGE & DEGREE OF HAZARD.

F & EI Range Degree of Hazard

0 – 60. Light.

61 – 96. Moderate.

97 – 127. Intermediate.

128 – 158. Heavy.

159 – and above. Severe.

43

DOW FIRE & EXPLOSION INDEX WORKSHEET

PLANT: PLANT AREA.MATERIALS AND PROCESS: BROMINE.MATERIAL FACTOR: 1

PENALTY FACTORRANGE

PENALTY FACTORUSED

1. GENERAL PROCESS HAZARDS.Base Factor. 1.0 1.0

A. Exothermic Chemical Reactions. 0.30 to 1.25 00B. Endothermic Process. 0.20 to 0.40 00C. Material Handling & Transfer. 0.25 to 1.05 0.6D. Enclosed or Indoor Process Unit. 0.25 to 0.90 00E. Access. 0.20 to 0.35 00F. Drainage and Spill Control. 0.25 to 0.50 0.0

General Process Hazards Factor (F1). – 1.6

2. SPECIAL PROCESS HAZARDS.Base Factor. 1.0 1.0

A. Toxic Materials. 0.20 to 0.80 0.6B. Sub – Atmospheric Pressure. 0.50 00C. Operation in or Near Flammable Range Inerted. – –

1. Tank Farm Storage Flammable Liquids. 0.0 –2. Process Upset or Purge Failure. 0.3 –3. Always in Flammable Range. – –

D. Dust Explosion. 0.25 to 2.0 00E. Pressure Operating atmospheric; Relief Setting. – 00F. Low Temperature. 0.20 to 0.50 00G. Quantity of Flammable/ Unstable Material Quantity

20 kl., Hc = 0.0 103 BTU/Lb.– –

1. Liquid or Gases in Process. – –2. Liquid or gases in Storage. – –3. Combustible Solids in Storage. – –

H. Corrosion and Erosion. 0.10 to 0.75 0.3I. Leakage – Joint and packing. 0.10 to 1.50 0.1J. Use of fired heaters. – 00K. Hot Oil Heat Exchange System. 0.15 to 1.15 00L. Rotating Equipment. 0.5 00

Special Process Hazards Factor (F2) – 2.0

Unit Hazards Factor (F1 F2 = F3). 3.2Fire and Explosion Index (F3 MF) (F & IE). 3.2THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 0.81 meterDAMAGE FACTOR. 0.04AREA OF EXPOSURE. 2.0 m2

T = [250 + 125 (1 + 1.6 + 2)]/100 = 8.25 T Cat II.

44

DOW FIRE & EXPLOSION INDEX WORKSHEET.PLANT: HYDROGEN CYLINDER SHED.MATERIALS AND PROCESS: HYDROGEN.MATERIAL FACTOR: 21

PENALTY FACTORRANGE

PENALTY FACTORUSED

1. GENERAL PROCESS HAZARDSBase Factor. 1.0 1.0


General Process Hazards Factor (F1). 1.5

2. SPECIAL PROCESS HAZARDSBase Factor. 1.0 1.0


1. Tank Farm Storage Flammable Liquids. 0.0 –2. Process Upset or Purge Failure. 0.3 0.33. Always in Flammable Range. – –

D. Dust Explosion. 0.25 to 2.0 00E. Pressure Operating 75 psig; Relief Setting + 10 %. – 0.39F. Low Temperature. 0.20 to 0.50 00G. Quantity of Flammable/ Unstable Material Quantity

80 cylinders, Hc 51.6 103 BTU/Lb.– –

1. Liquid or Gases in Process. – –2. Liquid or gases in Storage. – < 0.13. Combustible Solids in Storage. – –

H. Corrosion and Erosion. 0.10 to 0.75 0.1I. Leakage – Joint and packing. 0.10 to 1.50 0.1J. Use of fired heaters. – 00K. Hot Oil Heat Exchange system > 210 ft. 0.15 to 1.15 00L. Rotating Equipment. 0.5 00

Special Process Hazards Factor (F2) 1.89

Unit Hazards Factor (F1 F2 = F3). 2.84Fire and Explosion Index (F3 MF) (F & IE). 59THE DEGREE OF HAZARD MODERATERADIUS OF EXPOSURE 15 meterDAMAGE FACTOR 0.58AREA OF EXPOSURE 706 m2

45

DOW FIRE & EXPLOSION INDEX WORKSHEET.

PLANT: TANK FARM.MATERIALS AND PROCESS: TolueneMATERIAL FACTOR: 16

PENALTY FACTORRANGE

PENALTY FACTORUSED

1. GENERAL PROCESS HAZARDS.Base Factor. 1.0 1.0


General Process Hazards Factor (F1). – 1.25

2. SPECIAL PROCESS HAZARDS.Base Factor. 1.0 1.0


1. Tank Farm Storage Flammable Liquids. 0.0 –2. Process Upset or Purge Failure. 0.3 –3. Always in Flammable Range. – –

D. Dust Explosion. 0.25 to 2.0 00E. Pressure Operating atmospheric; Relief Setting. 00F. Low Temperature. 0.20 to 0.50 00G. Quantity of Flammable/ Unstable Material Quantity

10 kl ., Hc = 17.4 103 BTU/Lb.– –

1. Liquid or Gases in Process. – –2. Liquid or gases in Storage. – 0.313. Combustible Solids in Storage. – –

H. Corrosion and Erosion. 0.10 to 0.75 0.1I. Leakage – Joint and packing. 0.10 to 1.50 0.1J. Use of fired heaters. – 00K. Hot Oil Heat Exchange system > 210 ft. 0.15 to 1.15 00L. Rotating Equipment. 0.5 00

Special Process Hazards Factor (F2) – 1.91

Unit Hazards Factor (F1 F2 = F3). 2.38Fire and Explosion Index (F3 MF) (F & IE). 38THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 9.7 meterDAMAGE FACTOR. 0.35AREA OF EXPOSURE. 295 m2

T = {125+75×(1 + 1.25 + 1.95)}/100 = 4.40 T Category I

46

2.9

HAZOP STUDY

At

HIKAL LIMITEDPlot No.: A-18 MIDC Mahad,

DIST.:- RAIGAD, MAHARASHTRA , INDIA.

MARCH 2017

47

CONTENTS

SECTION DESCRIPTIONPAGE

NO.

2.9.1 HAZOP Methodology. 47

2.9.2 Process Description ,Flow Chart , Material Balance 55

2.9.3 HAZOP Worksheets

NODE 1: Tank Farm. 79

NODE 2: Halogenation 84

Sub node 2.1 : Bromine storage and handling 85

Sub node 2.2 : Process operations 89

NODE 3: Hydrogenation 97

Sub node 3.1 : Hydrogen cylinder trolleyhandling

98

Sub node 3.2 : Process operations 101

NODE 4: Esterification 106

NODE 5: Hydrolysis 110

NODE 6: Other unit processes and operations 114

NODE 7 :ETP 124

2.9.4 Compatibility/ Reactivity Hazards 129

48

2.9.1 HAZOP METHODOLOGYHAZOP

Safety and reliability of a modern processing plant can be improved by use of procedures that

recognize and eliminate potential problems in the design stage. Hazard Operability study is

now used to great satisfaction throughout the chemical industries.

It is based upon the supposition that most problems are missed because of a lack of

knowledge on the part of the design team. It can be used to examine preliminary process

design flow sheet at the start of a project or detailed piping and instrument diagrams at the

final design phase and during modifications of the existing plants.

In essence, it is an abbreviated form of "critical examination” based on the principle that a

problem can only arise when there is a deviation from what is normally expected. The

procedure, therefore, is to search the proposed scheme systematically for every conceivable

deviation, and then look backwards for possible causes and forwards for the possible

consequences.

DATA COLLECTION

49

Process description broken into steps & sub steps. Process flow diagram. Factory layout. Block-diagram of the plant equipment. P & I diagram of concerned equipment's. Material safety data sheets summary. Equipment specification & history.

HAZOP COMMITTEE

The HAZOP committee is formed as per following guidelines

CHAIRMAN OCCUPIER / FACTORY MANAGER.

CO –ORDINATOR Safety officer.

MODERATOR He is an expert in the HAZOP technique, not the plant; His job is toensure that the team follows the procedure. He needs to be skilled inleading a team of people who are not responsible to him and should bethe sort of person who pays meticulous attention to detail and cancontribute wherever needed.

PROJECT or DESIGNENGINEER For a new design

MAINTENANCE MANAGERFor operating plant

Usually a mechanical engineer and, at this stage of the project, theperson responsible for keeping the costs within the sum sanctioned. Hewants to minimize changes but at the same time wants to find outrather than later if there are any unknown hazards or operatingproblems.

PROCESS ENGINEER Usually the chemical engineer who drew up the flow sheet.

PLANT MANAGER Usually a chemical engineer, he will have to start up and operate theplant and is therefore inclined to press for any changes that will makelife easier.

INSTRUMENT /DESIGNENGINEER

As modern plants contains sophisticated control and trip systems andas HAZOP often result in the addition of yet more instrumentation to theplant.

RESEARCH CHEMIST If new chemistry is involved.

STUDY PROCEDURE

The procedure involves examining the model systematically, section by section or line by line

(depending on the level of detail required), looking for inadequacies in design. A checklist of

guidewords is applied to each stage of the process in turn, thereby generating deviations

opposites all conceivable eventualities.

50

Typical aspects considered are normal plant operation, foreseeable changes in normal

operation plant start-up and start- down, suitability of plant materials, equipment and instru-

mentation provisions for failure of plant services, provision for maintenance safety etc.

The possible causes and consequences of each deviation so generated are then considered and

potential problems thereby identified and noted if they merit action. The need for action is

decided semi quantitatively by taking into account both the seriousness of the consequence

and the probability of the events occurring. For any major risk area a quantitative hazard

analysis is also carried out.

The stage in the procedure are next considered for the case where a detailed line by line

examination is required. If any member of the study team is not familiar with the technique

an introductory talk and illustration is desirable before commencement of the study. Before

examining each section of the project, a team member summarizes the function of the section,

including normal process conditions and specifications if available to ensure that all team

members have the necessary background knowledge of the process.

All guidewords are then applied in turn on a line-by-line basis there by including process

deviations, e.g. no flow. They thus serve as an agenda to ensure that all aspects of plant

operation are considered and also force consideration of the lines joining items of equipment

or connecting the equipment to off sites and not directly to the equipment itself. This is

because any problem that could arise in a piece of equipment should show up as a cause or

consequence of a deviation in a line joined to that piece of equipment. However, the

guideword “OTHER” which has special significance for aspects other than normal operation

must be applied to items of equipment as well as the lines.

MEANING OF THE GUIDE WORDS

The following list, illustrate the types of deviation generated by each guide word (in capital

letters):

NONE: No flow, reverse flow, i.e. no forward flow when there should be.MORE OF: More of flow, temperature, pressure, viscosity etc. higher flow, higher

temperature, or whatsoever than there should be.LESS OFF: Lower flow, temperature, pressure, Viscosity, etc. than there should be.PART OF: Changes in compositions of the stream, e.g. ratio of components different from

what it should be.MORE THAN:Impurities present, e.g. ingress of air, water, acids extra phase present, e.g.

vapor, solids.

51

OTHER: What else part from normal operations can happen, e.g. start-up, shutdown,maintenance, catalyst change, failure of plant services.

Guide words are applied to the design intention tells us what the equipment is expected to do.

Each guideword was applied to the relevant parameter under examination of a sub step to

form a deviation. GUIDE WORDS helps in identifying the relevance of parameter for risk

assessment.

Thus for each section, the team determined the applicable parameter / guide word

combinations or deviations. Then for each deviation that could realistically occur, the team

members brainstormed causes of the deviation. For each cause, consequences and safeguards

were described. Consequences included fire, explosion, and release of flammable or toxic

material & operating problems; while safeguards were those that help to prevent the cause of

hazard or that mitigates the consequences of the hazard. In specific cases, safeguards also

included precautionary steps in written procedures. Apart from these recommendations,

whenever team members felt the need for further improvement, further study was

recommended considering the probability and seriousness of the hazard Recommendations

were for installation of procedures or administrative controls, of additional study to determine

an optional solution or whether a problem exists which warrants any action.

The creative state in the procedure is the recognition of possible causes and consequences of

each deviation generated by the guidewords. This relies entirely on the knowledge,

experience and expertise of the team and on an attitude of mind which looks for what could

go wrong in every conceivable eventuality. It must be thorough and exhaustive. For example

where provision has been made for a contingency, it must be questioned whether the provi-

sion is adequate (e.g. is a single non-return valve sufficient, do we need a high level alarm as

well as a level indicator, is the trip system reliable and of the right type, is the vent large

enough etc.)

Potential problems, as represented by the consequences of the deviations, should be evaluated

as they arise, and a decision reached on whether they merit further consideration or action.

Except for major risk areas where a fully quantitative assessment is required, this decision is

made semi-quantitatively on the basis of both the seriousness of the consequence (usually

scaled as trivial, important or every serious) and the frequency of the event (unlikely,

occasionally or every probable).

52

In some cases, the need for further action is clear-cut and the best remedy fairly obvious, e.g.

install a non-return valve to prevent back-flow. An action can then be quickly agreed and

recorded, before the study moves on to the next point.

In other instances, where the need for action is again very clear but a satisfactory solution not

immediately apparent, the team should avoid. It is sufficient to note the point as requiring

further consideration outside the study meeting before moving on the to the next item. Also,

if it is not possible to agree on whether or not any further action is required, either because

the problem is of borderline significance or because further information is required, the point

should again be recorded for attention outside the meeting.

DOCUMENTATION

The worksheet, the basic documentation of the team deliberations, consists of the following

details:

HAZOP STUDY : This consist of description in short of the process used or themanufacture of final product.

LOCATION/PLANT : This is obviously the place where the product is manufactured.

P & IREFERENCE

: This refers to the concerned P & I drawing number used forparticular operating step.

OPERATING STEP : Description of the step in the manufacturing procedure.

DESIGNINTENTION

: This actually is the sub step which describes the intention ofthe sub step.

UNIT/EQUIPMENT

: The name /number of the unit used for the sub steps.

GUIDE WORD : These are the words which are to be applied to intentions forasking questions for deviations. These are already wellexplained in above portion of this chapter. There can be manydeviation.

CAUSE (S) : Each of the deviation as mentioned above can have manycauses. These are mentioned in front of that deviation.

CONSEQUENCE : This is the cumulative effect of all or few deviations and aredescribed as number of consequences.

S/P/R : For each cause there is specified probability and seriousnessassociated with each deviation. The probability an seriousnessindividually needs to be judged quantitatively on the

53

predetermined scale. Considering the level of consequencesfrom 1 to 5 and probability levels as 1 to 5 determined bysafety philosophy and past experience of the HAZOPcommittee arrive at risk value index of level 1 to 10 for eachidentified hazard. The highest is indicated in the scale used.

ACTION : This is very important aspect and needs detail consideration.The actions are to be suggested for all those consequencesexcept which fall as low class as far as probability and seri-ousness are concerned. While considering actions manypoints are to be debated to find a solution which is costeffective and removes root cause, so that the deviation doesnot occur or at lest it reduces the probability and/orseriousness.

BY : This specifies who is expected to take action (preferably oneof the team members) and by what time the action will becompleted. Actually this needs management's concurrence asthe time & money is the main constrains in the action plan.

OPEN QUESTIONS : In this column as mentioned in the earlier portion of thechapter, if further study is to be done it has to be mentioned asto what is expected from the experiments/data to be collected.Few can be done immediately as in our case or few may needlonger period of experimenting.

Thus the total work sheet is filled as described above anddocumented in. Further for each step, there is a need to have asummary sheet of the actions to be taken. These needs to besummarized in a single sheet as 'Recommendations from“HAZOP”. Here detail description of the weakness observedduring the study and the recommendations made aredescribed. This helps management to get a view of the studyin a nutshell without going through the volume of Hazardworksheets. Many actions on worksheet are repeated & henceone can cover many deviations on one sheet.

Regular HAZOP meetings were carried out at factory. The HAZOP methodology adopted

was explained to the members of the committee in the opening session followed by updating

of P & ID for the plant. This enabled the team members to observe the equipment's layout,

note environmental conditions and obtain a mental picture of the facility. Although the team

members were familiar with the facility, they took the survey from different perspective.

Along with the drawings, documents were verified and corrected on the spot. These corrected

copies were used for the “HAZOP” Study.

54

The “HAZOP” was then conducted for each section using the guidewords, which were fully

explained to the team. As the study proceeded a review of the past incidents were taken at

appropriate intervals. Recording each session’s work in a “HAZOP” worksheet carried out

the table work of conducting the study. The documentation indicates: -

Which segment of process or procedure were reviewed?

Which guide words & parameters were considered?

The cause and consequences of each deviation studied.

Whether a potential problem exists?

What are the existing safeguards?

If there was a potential problem, the team recommended action to address the problem In

case of uncovered potential problems, the team recommended follows up & resolution of the

problem outside the “HAZOP” study to avoid spending of significant time. If the solution of

the problem was obvious the team documented their recommended solution. The total work is

documented as “HAZOP WORKSHEET”.

STUDY RESULTS/ FINDINGS

The success of the study is completely dependent upon there being an effective system for the

progressing of the points raised in the study and for implementing as appropriate. Ideally, the

implementing authority, e.g. the project manager should be represented on the study team to

gain commitment and to avoid having to explain points raised at the study meetings. This is

particularly important if more than one department’s are involved in implementation.

Alternatively, progressing of the actions can be carried out at separate meetings attended by

the project manager and or engineer and the individual study team member responsible.

Qualitative Assessment of hazards is carried out based on probability and seriousness while

working out action plan based on experience of the HAZOP TEAM and past performance of

the plant. Number of weaknesses leading to hazards are identified and summarized and

recorded.

HAZARD RATING METHODOLOGY

Step 1 : Estimate the probability of each hazard according to its likelihood of occurrence(very likely; likely; quite possible; possible; not likely) and assign thequantitative value accordingly.

55

Step 2 : Estimate the severity of each hazard according to its potential for harm (veryhigh, high; moderate; slight; nil) and assign the quantitative value accordingly.

Step 3 : Once the probability and the severity of the hazard are determined, as perfollowing table;

HAZARD PROBABILITY & SEVERITY RATING.

Hazard Probability Value Hazard Severity Value

Very Likely. 5 Very High. 5Likely. 4 High. 4Quite Possible. 3 Moderate. 3Possible. 2 Slight. 2Not Likely. 1 Nil. 1

HAZARD RATING

By multiplying these two factors i.e. probability and severity, a range of risk ratings between

1 and 25 is obtained.

HAZARD RATING MATRIX.

SEVERITY

PR

OB

AB

ILIT

Y

Very High(5)

High.(4)

Moderate(3)

Slight(2)

Nil.(1)

Very Likely. (5) 25 20 15 10 05

Likely. (4) 20 16 12 08 04

Quite Possible. (3) 15 12 09 06 03

Possible. (2) 10 08 06 04 02

Not Likely. (1) 05 04 03 02 01

Step 4 : According to the rating of each risk, it is necessary to evaluate it according to the

following.

Urgent situations (16 to 25) that require action immediately. High-risk situations (10 to 15) that require action in the short and medium-

term. Medium-risk situations (5 to 9) that require action or further evaluation within

an appropriate period. Low-risk situations (less than 5) that may require relatively little or no action.

Step 5 : Decide on the priorities for action and allocate resources to areas where they are

likely to have the greatest impact.

56

2.9.2 PROCESS DESCRIPTION ,FLOW CHART & MATERIALBALANCE

Sr. No. Product Page number

1 Ethyclozate 56

2 Amitrol Eliminated

3 5 Methoxy methyl Pyridine 2 , 3 Dicarboxyalic acid 60

4 Diuron 62

5 Sodium Hypochloride Eliminated

6 3,5 Dichloroaniline 63

72 Amino 2 Methyl isopropyloxy 6 methylpropiophenone

64

8 4 acetoxy 6 tert butyl 8 floro 2 3 dimethyle quinoline 67

9 Benefuresate 69

10 Benzophenaf 70

11 Clothianidin 71

12 Trifloxystrobin 72

13 Azoxystrobin 73

14 Thiacloprid 73

15 SMPGM 73

16 Fludioxanil 75

57

Process Description

1. Ethyclozate

Comp-I

Malonic Acid,Ammonium Formate,CNBA and Formic Acid will be added in the reactor

(Reaction-I @60-70°c). Then again 23% HCL,Water charge, MIBKwill be added for

carrying the reaction and the MIBL layer is to be obtained from the process. After the

completion of the reaction water for MIBK solution and water wash to such organic layer

will be transferred for MIBL recovery and Layer Separation.Aq goes to ETP.then charge

MIBK return & 25% caustic solution around for pH adjustment.(Reaction-90-95°c &

Reaction-III 115-120°c, Layer separation 110°c) After the reaction carried out the whole

mass being transferred in ANF for water washing and water & ML goes to ETP.Then the wet

cake Obtained.

Comp-II

Water,C.s.lye,Comp-I wet cake,Act. Carbon,water and Hydrazine Hydrate will be added in

the reactor for carrying the reaction is to be Distilled amount of MIBL and Aq. Qty. from the

process. After the completion of the reaction the whole mass will be transferred for

Crystallization using 30% HCL. The mass is wash with water I,II,III Filter with Hyflow.and

aqueous goes to ETP. Then the mass transferred for drying in the dryer and to get Product.

Comp-III

Compound II, Ethanol, H2So4 (98%) and 25% NaOH soln is added to Reaction @ 78-80°C,

Reflux for 6hrs and pH is adjustment to 4-5 below 25°C.Transfer the material to Sparkler

filter for Ethanol wash various types of filtration take place then add 5% sodium bicarbonate

solution for Concentration U/V below 35°C.Adjust Density,cool to 19-21°C, pH adjust to

8.Crystallization 18-20°C byusing water, then Ethanol and Water Wash is given to filter cake

in ANF-Filtration, Filtrate ML+ Water goes to ETP and Ethanol is recovered.Then the wet

cake is transferred for drying in the dryer to get Product.

58

Material balance

61

3 5 Methoxy methyl Pyridine 2 , 3 Dicarboxyalic acid (MMPDC)

Step I: -

DME mixture will be prepared in reactor. In this (Vazo Solution)Vazo and EDC will be

added. Then again added Bromine,15% NaOH, Recycle EDC and water in 15% NaOH will

be Bromination reaction take placeand Aq. layer obtained.

Step-II:-

Charging of raw material TMA,EDC and water for Quarternization reaction will be carried

in reactor. In this reactor again added MeOH, 48% NaOH & water in 48% NaOH For

methoxylation reaction and methanol Stripping. Then Recycle EDC carried out and theAq.

goes to ETP.

Step-III: - After such Process 93% H2SO4 added for Crystallization then Filtration, THF

Extraction and THF Distillation Process to be carried out.

Step-IV: - Crop-I & Crop-II wet material ttransferred for drying in the dryer.To get Product.

Material balance

63

4 Diiuron

In the process of the Diuron manufacturing the toluene is being added in the reactor.

Then 3, 4 DCPI being added in the reactor after the dehydration the DMA water 40 % being

added in the reaction.After the reaction carried out the whole mass being transferred in filter

for the filtration.The mass is being flush with water & aqueous goes to ETP, Toluene is being

recovered.Then the wet cake from the filter is dried in the dryer.

Material Balance

64

6 3,5 Dichloroaniline (3,5 DCA)

Stage IPreparation of 2, 6 DCPNA

In presence of hydrochloric acid PNA is reacted with chlorine gas to yield 2,6 DCPNA. The

mass is then filtered. Wet cake is basified, washed and kept ready for next stage. The filtrate

is recycled in next chlorination.

Stage IIPreparation of 3,5 DCNB

2,6 DCPNA is treated with sulphuric acid and sodium nitrate solution in presence of

Isopropyl alcohol. During the reaction acetone is formed as a byproduct and distilled out

along with Isopropylalcohole. 3,5 DCNB formed is filtered and wet cake is used in next

reaction.

Stage IIIPreparation of 3, 5 DCA

3,5 DCNB in presence of toluene and Raney Nickel catalyst is treated with Hydrogen gas to

yield 3,5 DCA. Then the mass is heated to distill out toluene and 3,5 DCA remained is either

stored in storage tank or packed in drums.

Material Balance

65

7 Amino 2 Methyl isopropyloxy 6 methyl propiophenone (APP)

Step 1:

AZPP: - Preparation of azide solution will be prepared. Then charge PRO, CPP & TBAB at 80-850 c.

Cool at 50 0 c. Separate the Aq. Layer and filter through activated carbon and wash material with

toluene after filtration will get AZPP.

Step 2:

APP: - Hydrogenation of AZPP and toluene will be conducted in hydrogenation reactor by addition of

PD catalyst. Give the toluene wash to the material and after filtration will get APP.

66

Material Balance:

68

8 4 acetoxy 6 tert butyl 8 floro 2 3 dimethyle quinoline(AF 02)

Step 1:- AMI –

Sodium Hydroxide 30% solution will be prepared in reactor. In this methanol and TBU will

be added under stirring at 25-30 0c. After cooling reaction mass extraction will be done and

finally filtration of organic layer through filter.

Step 2:- EMI - QUN:-

Charging of raw material at 75-80 0 c will be carried in reactor. In this reactor mass charge

Triethyl amine at 25-30 0 c. Diphenyl ether, EMM addition will be carried. Then add toluene

at 175-180 0c. Filter the dry QUN through filter.

Step 3:- Charge raw material anhydride in 2-3 hr. Chill the reaction mass at 2-6 0 c. Add 0.6

N HCL and 2 % sodium bicarbonate. Adjust the Ph 8-8.2. Add dist. Water at 25-30 0 c. Filter

the ML and separate the dry AF02.

Material Balance

70

9. Benefuresate

The sodium Hydroxide, NaBH4, NC9774 and water will be added in the reactor. After the

maintaining the toluene will be added. After the filtration the acidification reaction will be

carried for this the H2SO4 will be added. After the acidification mass will be filtered and

dried.

The TEA, PA & Water will be added for the reaction with above dried material, after this

water NaOH and xylene will be added for conducting reaction. The xylene wash is given and

this will be filtered. After this acidification and xylene distillation will be carried out and will

get final Benfuresate.

Material Balance

71

10 Benzophenaf

1. The MY710, PMPC and water will be added in the reactor for carrying reaction the

after maintaining the N hexane and H2SO4 will be added for carrying the reaction and

the N hexane is to be recovered from the process. After the completion of the reaction

the whole mass will be transferred in the filter. The mass is flushed with water and

methanol. The methanol will be recovered and aqueous goes to ETP. Then the mass

transferred for drying in the dryer.

Material Balance

72

11 Clothianidin

In the process of the Clothianidine manufacturing the Nitramide,Aq. MENH2 and MeOH isbeing added in the reactor at 55°C for 3hours.Then MeOHis being recovered and the waterwaste goes to ETP to get Product.Material Balance

12 Trifloxystrobin

In the process of the Trifloxystrobin manufacturing the Methoxyiminoacitic acid methyl ester

(2- bromomethyl phenyl),Methyl isobutyl ketone,Potassium carbonate and EthanoneOxime

(1-(3-trifluromethyl phenyl) is being added in the reactor.After the reaction carried out the

whole mass being transferred in filter for the filtration.Methyl isobutyl ketone is being

recovered and Product is obtained.

Material Balance

73

13. Azoxystrobin

The methyl-2-(2-(6 chloropyrimidine-4 yloxy ) phenyl)-3-methoxyacrelate,Potassium

carbonate,DMF, 1,4-diazobicyclo(2,2,2) Octane2-cyano phenolwill be added in the reactor

.After the reaction carried out the whole mass being transferred for the Distillation and DMF

is to be recovered from the process. Then added Toluene and carried out extraction Process.

Methanol will be recovered and aqueous goes to ETP. Then the mass transferred for drying in

the dryer.Then the wet cake from the filter is dried in the dryer and to get Product.

Material Balance

74

14 .ThiaclopridIn the process of the Thiaclopridmanufacturing the Cysteamine hydrochloride (72%

Solution),CDIM,Toluene,Soda Ash,CCMP and Water is being added in the reactor.After the

reaction carried out Add Methanol for Purification and obtain Product.

Material Balance

15 SMPGM

Stage-I:Acetophenone is reacted with sodium cyanide,Ammonium carbonate and methanol to give

the stage-I intermediate RS-Hydention. After pH adjustment with HCl,methanol is distilled and the

residual mass is filtered to isolate RS-Hydention.

Stage-II:RS-Hydention undergoes to form S-Hydention MBA salt by reaction with Alpha-MBA in

presence of caustic.S-Hydention MBA salt is isolated by filtration.Alpha MBA is recovered from S-

Hydention salt by distillation in presence of excess caustic. ML from filtration is treated with HCl and

filtered.Wet is further processed to recover S-Hydention from RS-Hydention.

Stage-III:S-Hydention is hydrolysed to form the sodium salt of amino acid

Stage-IV:Sodium salt of Amino acid formed undergoes esterification in presence of Sulphuric acid

methanol. Methanol distilled out from filtrate.The residual mass is given Na2CO3 wash and the Ester

is extracted into MonochloroBenzene.MBA is distilled off to get the Product.

75

Stage-V: Alpha MBA is Recovered from RS-Hydention salt by reaction with HCl followed by filtration.

The ML is treated with caustic and distilled to recover Alpha MBA.

Material Balance

76

16 Fludioxanil

Process description

Step-1:

Preparation of intermediate 2((Z)-2-Cyano-3-ethoxy-acrylic acid ethyl ester):

A solution of ethyl cynoacetate and triethylorthoformate in acetic anhydride was heated to

140 °C and stirred. The solvent was evaporated to afford crude intermediate 2 ((Z)-2-Cyano-

3-ethoxy-acrylic acid ethyl ester as a low melting solid.

Step-2:

Preparation of Intermediate 4 N-(p-tolylsulfonylmethyl) formamide:

Charged sodium p-toluenesulfonate and water, to this added aqueous 34–37% solution of

formaldehyde, formamide and formic acid and stirred the reaction mixture. Heated the

reaction mixture at 90°C. The reaction mixture was cooled to room temperature and then

further cooled to−20 °C. The white solid was collected by filtration and washed with ice

water. The product was dried under reduced pressure at 70 °C, and gave crude 4N-(p-

tolylsulfonylmethyl)formamide.

Step-3:

Preparation of Intermediate 5 (1-Isocyanomethanesulfonyl-4-methyl-benzene):

Charged crude N-(p-tolylsulfonylmethyl)formamide4, 1,2-dimethoxyethane, diethyl ether

and triethylamine. The stirred suspension was cooled. A solution of phosphorusoxychloride

in 1,2-dimethoxyethanewas added. Stirred the reaction mass. Filtered the precipitatedsolid

and washed with cold water. After workup yield dint 5as a light-brown odorless solid.

Step-4:

Preparation of Intermediate 7- (2, 2-dichloro-1, 3-benzodioxole)

Chargedbenzo [1, 3] dioxole6 and phosphorus pentachloride and heated at 98 °C–165 °C for

1.5 h. The reaction mixture was distilled under reduced pressure yielded 2,2-dichloro-1,3-

benzodioxole 7.

Step-5:

Preparation of Intermediate 8(2, 2-difluoro-1, 3-benzodioxole)

Charged KF, KHF2, tetramethylenesulfone and 2, 2-dichloro-1, 3-benzodioxole7. The

mixture was heated to 140°C under stirring for 8 h. The reaction mixture was cooled and to

77

this reaction mixture added water to dissolve the salts. The desired product 2,2-difluoro-1,3-

benzodioxole8 was separated was purified to gave 2,2-difluoro-1,3-benzodioxole 8.

Step-6:

Preparation of Intermediate 9:

Charged2,2-difluoro-1,3-benzodioxole8, hexane. To the reaction mixturewas added n-butyl

lithium (1.6 M in hexane) and TMEDA at −15 °C. To the resulting precipitate of 2,2-

difluoro-1,3-benzodioxole-4-yllithium was added a solution of ethoxymethylenecyanoacetic

acid ethyl ester 2 over a period of 30 min. at −20 °C. After stirring for 20 min. at −20 °C, the

reaction mixture was hydrolyzed using 2N HCl solution. After workup and

crystallizationfrom ethanol/ water (4:1)afforded desired Int.9.

Step-7:

Preparation of Fludioxanil (10):

ChargedInt. 5, ethyl acetate andInt. 9 at room temp. The mixture was cooled to 0–5°C and

35% NaOH solution in methanol was added drop wise over 1 h under stirring. The stirring

was continued further for 1 h at 20°C. Ethyl acetate and methanol mixture was removed by

distillation. After evaporationof solvent, water was added and the mixture was filtered, and

the filter residue washed with methanol/water mixture yielded Fludioxanil10.

Material Balance

HIKAL LIMITED A-18, MIDC Mahad

80

NODE 1: : TANK FARMDESIGN INTENT : Receipt, Storage & Transfer To Plant of petroleum class A,B,C class solvent

GUIDEWORD

PARAMETER DEVIATION CAUSE CONSEQUENCEPROTECTIONMEASURES

sS P R RECOMMENDATIONS

None. Flow. No flow ofsolventduring roadtankerunloading tostorage tankor transferto day tankfrom storagetank.

No material in theroad tanker orstorage tank.

Valve failure/blockage.

Line blockage.

Transfer pumpfailure (loss ofpower, impellercame off orcorroded etc.).Human error.

Delayed operation.

Delayed operation.

Spill hazard duringblockage removaloperation.Delayed operation.

Delayed operation.

LG.

Preventivemaintenance.

PPE.Training.


Supervision.

2

3

3

3

3

3

3

3

6

9

9

9

Log book record.

SOP for blockage removaloperation.

More. Flow. More flow ofsolventduringtransfer today tankfrom storagetank.

Valvemalfunctioning.

Human error.

Delayed operation. LI at storage tank.

Improvedsupervision.

3 3 9 Preventive maintenance.

NODE 1: : TANK FARM


81

DESIGN INTENT : Receipt, Storage & Transfer To Plant of petroleum class A,B,C class solvent

GUIDEWORD


S P R RECOMMENDATIONS

Less. Flow. Less flow ofSolventduringtransfer tofeed tankfrom storagetank.

Valvemalfunctioning.

Human error.

Delayed operation. LI at storage tank.

Improvedsupervision.


Reverse. Flow. Reverse flowof line holdup .

Power failureduring transfer toplant

Delayed operation. NRV in dischargeline.


As WellAs.

Flow. As well as. Rust, dirt etc. Disturbed operation. Strainer in supplyline.


Other. Flow. Staticcharge.

Static sensitivematerial Solventtransfer by pump.

Free fall ofSolvent in thetank

Static discharge assource of ignition in caseof any spill and vaporscoming in flammablerange with air.

Fire/ explosion hazard atsolvent tank farm

Supervision.

Dip pipe provided infeed lines.

Road tanker andtanks earthing &Bonding

4 4 16 Take precautionary measuresagainst electrostatic loading.

Other. Flow. Release ofliquid/vapors.

Pump land leak.

Gasket failure.

Sampling.

Vent release.

Spill selease of solventvapors.Formation of flammablemixture with air.Fire/ explosion hazard iffinds source of ignition.

Open area. 4 3 12 Monitor the work place air bornconcentration of chemicals withinprescribed limit.

Provide leak detection system.

NODE 1: : TANK FARM


82

DESIGN INTENT : Receipt, Storage & Transfer To Plant of petroleum class A,B,C class solvent

GUIDEWORD



Other. Flow. Large spill ofsolvent attank farm.

Failure of thevessel, tankeretc. Due toimpact/mechanicalfailure.

Leak due toexternalcorrosion of tank

Spill of flammable solventat tank farm

Fire/explosion hazard attank farm if the flammablevapors finds source ofignition.

Soil pollution

Supervision.

UG tank.

Curb wall forcontainment.

Corrosion resistmentpainting to externalsurface of buried tankFire fighting system.

5 4 20 Revise “On Site Emergency Plan”based on MCLS Study.

Consider periodic checking of soilcondition at the tank .

OtherThan.

Flow. Materialother thanintended intank.

Accidental mixup.

Human error.

Depends on the mix upcomponents.

Dedicated piping,hence, not likely.

Supervision.

Process ontrol check.

3 3 9

More. Temperature. Moretemperatureat Solventstoragetank.

Temperatureindicatormalfunctioning.

Release of vapors at vent. Supervision. 2 3 6 Regular calibration ofinstrumentation.

Less. Temperature. LessTemperature.

Winter season. Freezing not anticipated. 3 3 9 –


83


GUIDEWORD



More. Pressure. MorePressure.

More rate of pumpingin and vent blockage.

Vent blanked off.

Plastic bag over vent.Vent choked.

Flame arrestorchoked.

Vent connected towater seal.Vent too small.

Vent modified.

Flexible tubingconnected to vent.

In let of hot recycleliquid.

Pressurization. Vent inspection. 4 3 12 Preventive maintenance.

Less. Pressure. Lesspressure.

More rate of pumpingout and vent blockage.

Implosion hazard. Vent inspection. 4 3 12 Preventive maintenance.


84


GUIDEWORD



As WellAs.

Composition. Impurities. Contamination intanker.Supply source.

Disturbed operation. Dedicated piping.Process controlchecks.

3 2 6

More. Phase. Increase inphases.

Moisture/ waterin feed rain.

Disturbed operation/quality issue.

Rain cap at vent. 2 2 4

More. Level. More level. More feed inerror to day tank

Spill hazard. High level interlock infeed line.

5 3 15 SOP.

Less. Level. Less level. Less material inthe tank.

Starving of pump suction. Low level interlock infeed line.

3 3 9

Other. Handling. Cleaning ofthe piping/tank/equipments.

Inspection,repair,maintenancework.Externalcorrosion.

Residual vapors in theequipment/ piping firehazard.

Health hazard.

SOP.

Supervision.

3 3 9 Work permit.

Other Handling Accidental

mix up of

chemicals in

during

handling at

site .

Reactivity/compatibilityhazards due tolarge numberofchemicals atstore .

Unsafe condition

Depends upon mix up

components

Store located away

from tank farm .

4 4 16

85

NODE 2: Halogenation

Halogenation is a process of adding a halogen atom on an organic compound. (Halogen is

thecollective name for Fluorine, Chlorine, Bromine, And Iodine). Halogenation describes the

introduction of halogen atoms into an organic molecule by addition or substitution reactions.

In organic synthesis this may involve the addition of molecular halogens (e.g. Cl2, Br2, I2 or

F2) or hydrohalogenation (with HCl, HBr or HF) to carbon-carbon double bonds.

FLOW CHART

Aromate

HX

Aq or org solvent

HALOGENATIONS

VOC

HX

Precipitation

Filtration Mother liquor aqor

organic

Water Product washing Wash water

Solid product

86

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.1: BROMINE STORAGE & HANDLING.GuideWord

Parameter Deviation Cause Consequence Protection Measures S P R Action

Other. Flow Bromineleak

Bromine storageCorrosionPiping leak(Mild steel andstainless steel areNOT recommendedfor bromineservice.)

Spill in uncontrolled manner, healthhazard.

The readily identifiable color and

pungent odor gives immediate

warning of bromine’s presence. At a

concentration of only one part per

million (ppm), bromine is easily

detectable and even lesser amounts

can cause eye irritation. The OSHA

Permissible Exposure Limit (PEL) for

bromine is 0.1 ppm.

Supervision.Storage of Bromine in adry, well-ventilated area,protected from moistureand excessive heat orcold.SCBA and PPE

Note that Bromine is so

painful to the eyes, nose

and throat that it gives

ample warning of its

presence in acutely

hazardous

concentrations.

3 3 9 Provide leak detectors atstrategic locations at storage aswell as consumption point andscrubber vent with signal atcontrol room and ECC

A wind sock should be clearlyvisible from all points on the siteand replaced as required. Thisis required for indicating windstrength and direction.

Electrical installation:

Junction boxes and light fittingsshould be dust and vapor tight.

Do not use aluminum oraluminum alloys unless suitablycoated.

Use Totally Enclosed Fan Cooled(TEFC) motors of cast iron orsteel construction and epoxy-based coating.

87

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.1: BROMINE STORAGE & HANDLING.

GUIDEWORD


S P R ACTION

Signs should be posted prominently atthe site entrance and throughout theinstallation with area maps showingaccess ways, hydrant locations,emergency showers, location ofemergency equipment and emergencytelephone numbers.

Emergency respirator equipmentcabinets should be installed not morethan 30 meters or ten secondswalking distance from any location inthe storage area.

More Flow Bromine spill Storage tank spill dueto piping failure ,equipment failure

Loss of contentmentdispersion of Brominein down winddirection healthhazard.

Supervision. 5 4 20 Minimize the dispersal of brominevapors by locating the storage areaon low ground. Low curbs or walls(called dikes). 200 mm high, shouldenclose the storage area to protectthe area from external flooding and tominimize the dispersal of brominevapors. The minimum diked volumeshould be equivalent to the largeststorage tank plus 10%.

88

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.1: BROMINE STORAGE & HANDLING.Guide Word Parameter Deviation Cause Consequence Protection Measures S P R Action

Other. Emergency Bromine spill Storage tank spill dueto piping failure ,equipment failure

Exposure to Bromineduring spill controloperations , healthhazard.

Bromine is a verystrong oxidant. It isextremely toxic andmay prove fatal ifinhaled or swallowed.Severe burns mayresult from skincontact, and contactwith the eyes maycause blindness.

Supervision.Stock of

neutralizingmaterials such asSodium ThioSulphate stockSodium Meta BiSulphate, PotassiumCarbonate, SodiumCarbonate orSodium Bicarbonate.

Bromine handlingarea Floors ofimperviousconstruction.

5 4 20 The diked area should not have asewer connection. Provide anacequate size sump for collectingbromine spills and pump awaycollected rainwater and fire-fightingwater. Fire-fighting water should beprevented from contaminating watersources.There should be a strengthenedapproach way for emergency vehicleson two sides of the installation.There should be sufficient brominestorage tank capacity or an emptyisotank to accommodate the transferof bromine from a leaking container.

Revise “DMP” based on MCLS Analysisfor the site with dove tailing data foroffsite disaster control plan.See note 1 and Prepare SOP fordisposal of sand soaked with spill/waste generated during spill control.

As well as Composition

water ingress Rainy season See note 1 Supervision 3 3 9

89

NOTE 11. Reaction of bromine with water results in the formation of an aqueous solution of hydrobromic and hypobromous acids. The latter is relatively stable only in

solution, and decomposes under the influence of heat, light or copper catalysis to produce hydrobromic acid and oxygen.Br2 + H2O → HBr + HOBr

2. Reactions of bromine and ammonia occur readily, and depending upon temperature and pressure, produce nitrogen and hydrogen bromide, bromamines, andammonium bromide. The ammonium bromide forms as a result of the reaction between hydrogen bromide and excess ammonia present.

3. With strong alkalis at low temperatures in aqueous solutions, bromine reacts to produce bromide and hypobromite salts.

Br2 + 2 NaOH → NaBr + NaOBr + H2O

At elevated temperatures, the hypobromite undergoes an oxidation reduction reaction to produce bromate and bromide salts.

3 NaOBr → NaBrO3 + 2NaBr

The balanced summation of these two reaction equations yields:

3 Br2 + 6 NaOH → 5 NaBr + NaBrO3 + 3 H2O

4. Neutralization Dry bromates (products of sodium hydroxide neutralization of bromine) are powerful oxidants and are shock sensitive. They must be handled withextreme care.

5. Neutralization of bromine is extremely exothermic. It should be done slowly with sufficient external cooling capacities. Proper materials of construction of allequipment should be observed. Bromine is a strong oxidizer that reacts with some metals and is incompatible with many elastomers and plastics.

6. Neutralization with sodium bisulfite requires 3 moles of sodium hydroxide: 1 mole sodium bisulfite: 1 mole bromine.

7. Neutralization with sodium sulfite requires 2 moles sodium hydroxide: 1 mole sodium sulfite: 1 mole bromine.

8. The weights and volumes specified include a 10% excess of sodium hydroxide and sodium bisulfite or sodium sulfite. This excess should be observed.

9. This neutralization procedure is designed to assure that the final waste stream has been completely neutralized with respect to acidity and oxidation potential.

Br2 + Na2SO3 + 2NaOH 2NaBr + Na2SO4 + H2OBr2 + NaHSO3 + 3NaOH 2NaBr + Na2SO4 + 2H2

90

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.1: BROMINE STORAGE & HANDLING.

GUIDEWORD


S P R ACTION

As WellAs.

Solid waste. Disposal ofsolid wastegeneratedduring spillhandling.

Neutralization dryBromates (productsof Sodium Hydroxideneutralization ofBromine).Sand soaked withspill/ wastegenerated during spillcontrol.

Environmental issues. Hazardous solidwaste disposal toCHWTSDF.

3 3 9 Neutralization dry Bromates (productsof Sodium Hydroxide neutralization ofBromine) are powerful oxidants andare shock sensitive. They must behandled with extreme care.

More Temperature Moretemperature

Summer seasonLocal fire

Bromine is notcombustible butdecomposes onheating , releasingcorrosive and toxicgases

Fire hydrant system 3 3 9

Less Temperature Lesstemperature

Winter season Freezing not likely - - -


91

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.2: Process operations

GUIDEWORD


S P R ACTION

None. Flow. No flow. No flow of coolingmedium toHalogenationreactor.

Uncontrolledreaction.

Pressurization/explosion hazard.

SOP.

Supervision.

5 3 15

More. Flow. More flow. More flow –addition ofcontrolled reactante.gBromine ,Phosphrouspentachloride


SOP.

Supervision.

5 3 15

Less. Flow. Less flow. Less flow of coolingmedium to thereactor.


SOP.

Supervision.

5 3 15

Reverse Flow. Reverse flowat ventsystem.

Reverse flow at ventsystem as commonvent.

Disturbedoperation.

SOP.

Supervision.

3 3 9 In case here is common headersystem for vent consider positiveisolation of the any detrimentalstream considering reactivityhazard such precaution need to beincorporated in the SOP.


92

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.2: Process operationsGUIDEWORD

PARAMETER DEVIATION CAUSE CONSEQUENCE PROTECTION MEASURES S P R ACTION

AsWellAs.

Effluent. Effluentgeneration inHalogenation

operations.

Mother liquoraqueous ororganicwashings.

Environmental issues.

The biological degradabilityof halogenated hydrocarbons(especially aromatics)decreases as their halogencontent increases.

ETP 3 3 9

AsWellAs.

Emissions. Vent gases. VOC.Unreactedhalogen likeBrominehydro halogenlike HydrogenBromide

Health hazard due to vaporsemissions at work place.

Environmental issues.

The halogen content of thewaste gas pollution issues incase scrubber malfunctioningToxic gas release at vent incase of scrubber failure.

Scrubber.Vents of reactors, tankscollected and treated.Options; Product recovery (by

vapour stripping ofliquid streams followedby recycling to theprocess).

Scrubbing the acid gaswith an easilyhalogenated compound(preferably a rawmaterial used in theprocess).

5 4 20 Provide leak detectors atthe vent of scrubber toensure the performance ofthe scrubber or considersuitable interlocks.

Cont……..


93

NODE 2 OF 6 : HalogenationsDESIGN INTENT : SUB NODE 2.2: Process operationsGUIDEWORD

PARAMETER DEVIATION CAUSE CONSEQUENCE PROTECTION MEASURES S P R ACTION

AsWellAs.

Emissions. Vent gases. Scrubber malfunctioning(loss of circulatingsolution, power failureetc.)

Cont.. Absorbing the acid gas in waterto give aqueous acid (oftenfollowed by caustic scrubbingfor environmental protection).

Washing out organicconstituents with organicsolvents.

Condensing out organic by-products for use as feedstock inanother process.

5 4 20 Cont..

AsWellAs.

Solidwaste.

Soild wastedisposal.

Spent catalyst.Residue distillation.Residue unwantedisomers.

Environmentalissues.

Hazardous Solid waste disposal toCHWTSDF

3 3 9 SOP for residuestorage anddisposal by sendingto waste disposalfacility.


Static sensitive materialhandling.

Static charge assource of ignition,fire hazard.

Equipments are earthed 4 4 16


94


GUIDEWORD


S P R ACTION

Less. Temperature Lesstemperature

Low temperatureprocessrequirement.

Not significant. Stand by coolingarrangement.

– – –

More. Pressure. Morepressure.

Reaction exotherm.

Faster addition ofcontrolled reactant.

Accumulation ofreactant on loss ofturbulence.

Reaction exotherm–critical to control.

Accidental mix up.

Water reactivechemicalsdecomposition withwater.

Pressurization.

Explosion hazard atreactor due touncontrolledexothermicreactions.

SOP. 5 4 20 Provide adequate pressurerelief system (RD and dumptank) for the reactor carryingexothermic reactions to avoiduncontrolled release ofchemicals in case of accidentalpressurization.

All pressure safety valvesshould be set at 10 % higherthan the maximum achievableworking pressure.

Prepare “DMP/ On SiteEmergency Plan” based onMCLS Study.

Provide fire hydrant system.


95


GUIDEWORD


S P R ACTION

Less. Pressure. Lesspressure atreactor.

Vacuum in thesystem.

Fast pumping outand vent closed.

Fast cooling, ventclosed.

Not significant. Equipments aredesigned forvacuum.

– – –

More. Phase. Morephases.

Agitation loss (lossof power,mechanical problemetc.).

Layer separation.

Unsafe condition.

Explosion hazard onrestarting.

SOP.

Supervision.

3 3 9

As WellAs.

Composition Impurities. Impurities,intermediates, sidereaction productsand decompositionproducts byproducts.

Poorlybiodegradable andtoxic, environmentalissues.

Isomer control andseparation.

3 3 9 Obtain MSDS of impurities,intermediates, side reactionproducts and decompositionproducts (if any), in absence of theinformation the chemicals shouldbe treated as if hazardouschemicals.


96


GUIDEWORD


S P R ACTION

More. Level. Contamination Accidental mix up. Refer previoussection forcompatibility /reactivity hazards.

SOP.

Supervision.

3 3 9 Same equipments are used formore than one operation/ productstage hence, increases theprobability of deviations inoperation/ human error especiallyof unintentional mix up/contamination hence introduceproduct change over SOP .

Less. Level. More level. Human error.Excessive chargingof batch.

Entrainment,ingress of materialin vent line.

Sight glass/ glassequipment.

3 3 9 Provide vacuum trap in vacuumline.

Other. Handling. Less level. Less batchcharging.Human error.

Thermowell maynot dip.Unsafe condition.

SOP.

Supervision.

3 3 9

Other. Handling. Handling ofphosphrouspentachloride

It is is waterreactive chemical

Corrosion.

Health hazard.

SOP.

Supervision.

4 3 12 Safety precautions for fire fightinginvolving water reactivee chemicals


97


GUIDEWORD


S P R ACTION

Other. Handling. Corrosion. Acidic streams arecorrosive.

Corrosion. MOC of anyequipment incontact with acidgases and waterconstructed inacid-resistantmaterials orinternally coated.

3 3 9

As WellAs.

Solid waste. Disposal ofsolid wastegeneratedduring spillhandling.

Neutralization dryBromates (productsof SodiumHydroxideneutralization ofBromine).

Sand soaked withspill/ wastegenerated duringspill control.


Hazardous solidwaste disposal toCHWTSDF.

3 3 9 Neutralization dry Bromates(products of Sodium Hydroxideneutralization of Bromine) arepowerful oxidants and are shocksensitive. They must be handledwith extreme care.

Prepare SOP for disposal of sandsoaked with spill/ waste generatedduring spill control.

98

NODE 3: Hydrogenation

Catalytic Hydrogenation refers to the addition of Hydrogen to an organic molecule in the

presence of a catalyst. It can involve direct addition of Hydrogen to the double bond of an

unsaturated molecule; amine formation by the replacement of Oxygen in Nitrogen containing

compounds; and alcohol production by addition to Aldehydes and Ketones.

FLOW CHARTHydrogen

Organic

Catalyst

HYDROGENATION.

VOC.

Hydrogen. unreacted.

Filtration. → Spent catalyst.

Purification. → Residue.

Product.

Typical sequence of operations for hydrogenation.(Inputs on left and waste streams on right with colored background).


99

NODE 3 OF 6 : HYDROGENATIONS. Sub node 3.1 : Hydrogen cylinder trolley handlingDESIGNINTENT

: Hydrogen cylinder trolley storage shed.

GuideWord Parameter Deviation Cause Consequence

ProtectionMeasures S P R Action Suggested

None. Flow. No flow. No material in

the cylinders.

Isolation valve

failure, closed in

error.

PRV

malfunctioning.

Delayed

operation.

PI provided.

Preventive

maintenance.

2 2 4

Less. Flow. Less flow. Leak transfer

line blockage/

leak.

Release of

Hydrogen. Fire

and explosion

hazard at

Hydrogen

cylinder storage

installation.

SOP. 4 4 1

6

Hydrogen leak detector.


100





Other. Flow.Staticcharge.

Higher flowrates.

Static charge assource of ignition,fire/ explosionhazard.

Earthing andbonding.

Flameproofelectrical.

5 420

Provide effectivemeasures for preventionof accumulation of staticcharge to a dangerouslevel.

Other. Flow. Loss ofcontainment.

Catastrophicfailure ofcylinderinvolved in localfire.

Fire/ explosion. Fire hydrantsystem.

FEA.

5 4 20

DMP and Mock drill.

Water sprinkler.

Avoid uncontrolledgrowth of vegetation nearshed.

More. Temperature.

Moretemperature.

Summer season. Pressuredevelopment.

Shed for storage ofcylinders/ trolley.

5 3 15

Less. Temperature.

Lesstemperature.

No potentialproblemsidentified.

1 1 1


PRVmalfunctioning.

Pressuredevelopmentgasket leak.


3 3 9 Regular calibration andinspection.


101







2 2 4

OtherThan.

Composition.

Nitrogenqualitypoor.

Commissioningof plant as inertgas. For lineflushing ifNitrogen isreplaced byOxygen.

Explosion hazard. Oxygen meter totest quality ofNitrogen.

5 3 15


102

NODE 3 OF 6 : HYDROGENATIONS. Sub node 3.2 Process operationsDESIGNINTENT

: Hydrogenation product process operations



None. Flow. No flow. No flow ofcooling mediumtoHydrogenationreactor.


Pressurization /explosion hazard.

SOP.

Supervision.

5 3 15

More. Flow. More flow. More flow ofHydrogen.

Release ofunreactedHydrogen at vent/pressurization.

Vent. 5 3 15

Provide flame arrestor invent of Hydrogen ventsand locate flame arrestorsat to convenient place forease of maintenance.

Less. Flow. Less flow. Less flow ofcooling mediumto nitrationreactor.


SOP.

Supervision.

5 3 15

Reverse. Flow. Reverseflow.

Reverse flow atHydrogen feedline.

Dip pipe in thereactor, feed linefracture, siphon.

NRV in Hydrogenfeed line.

4 3 12

As WellAs.

Flow. Effluentgenerationin processoperation.

Waste waterstreams fromprocess.


ETP provided. 3 3 9


103

NODE 3 OF 6 : HYDROGENATIONS. Sub node 3.2 Process operationsDESIGN INTENT : Hydrogenation product process operations



As WellAs.

Flow. Vent gases. VOC.Hydrogenunreacted.

EmissionsEnvironmentalissues.

Flame arrestor.

Leak detector.

3 3 9

Other. Flow. Staticchargegeneration.

Handling ofstatic sensitivematerials such asHydrogen.

Fire / explosionhazard.

Flameproofelectricalconfirming to ClassIIC for Hydrogen.

3 3 9 Provide effectivemeasures for preventionof accumulation of staticcharge to a dangerousextent.

OtherThan.

Flow. Mix up. Not anticipated. Closed piping. – – –

More. Temperature.

Moretemperature.

More rate ofaddition ofHydrogen.

Temperature riseas Hydrogenationis an exothermicreaction.

Hydrogenation isan mild exothermicreaction and theequilibrium usuallylies far towards theHydrogenatedproduct under mostoperatingtemperatures.

3 3 9

Less. Temperature.

Lesstemperature.

Low temperatureprocessrequirement.

Not significant. TI. – – –

More. Pressure. Morepressure atreactor.

Reactionexotherm.PRV failure,more feed in

Pressurization.

Explosion hazard..

SOP.

Generally Reactionexotherm for

4 4 16

Provide adequatepressure relief system(RD and dump tank)forHydrogenator .


104




error, accidentalmix up, utilityfailure etc.

Catastrophicfailure of reactor

Hydrogenations ismild.

All pressure safetyvalves should be set at10 % higher than themaximum achievableworking pressure.Prepare “DMP / OnSite Emergency Plan”based on MCLS Study.Provide fire hydrantsystem.



Fast pumpingout and ventclosed.

Fast cooling,vent closed.


– – –

OtherThan.

Composition.

Other thandesiredmaterial.

Oxygen inNitrogencylinder in error.

Fire / explosionhazard.

Supervision. 5 3 15 Check the purity ofNitrogen cylinder (forOxygen) in caseNitrogen cylinder isused for inerting.


105




As WellAs.

Composition.

Impurities.Side reactionproducts.

Quality issues.

Hydrogenationreactions generatelittle or nounwanted by-products.

3 3 9

More. Phase.Morephases.

Gas – liquidphase process.

Not significant. – – –

More. Level. More level. Human error.

Excessivecharging ofbatch.

Entrainment,ingress ofmaterial in ventline.


3 3 9 Provide vacuum trap invacuum line.

Less. Level. Less level. Less batchcharging.

Human error.

Thermowell maynot dip.

Unsafe condition.

SOP.

Supervision.

3 3 9

Other. Handling. Hydrogencylinderabuse instorage &handling.

Hydrogencylinderhandling.

Leak valvefailure/ pipingfailure.

Local fire.

Hydroegn release.

Fire/ explosionhazard.

Flame proofelectrical.

5 4 20

Provide shed for storageof Hydrogen cylinder,water sprinkler Firehydrant system.

Training to employees.

Provide Hydrogen leakdetector.


106




Other. Handling. Emergency. Hydrogen iscombustible inair and Oxygenover widerconcentrationlimits than mostother gases.

Flammablemixtures in aconfined spacewill explode ifignited by a flameor spark.

Fire/explosion.

4 3 12

Other. Handling. Solventstorage andhandling.

Solvents areused atprocessing suchas Methanol ,Toluene ,process 3,5DCAstage III

Leak, spill hazardof the flammablesolvents atstorage or atplant. Fire/explosion hazard.

Flameproofelectrical.

Supervision.

Fire extinguishers.

4 3 12

Provide fire hydrantsystem.

Other. Handling. Solid wastedisposal.

SpentHydrogenationcatalyst.


The spent catalystsare sometimestreated as wastes/sometimesreclaimed forrecycle.


3 3 9

107

NODE 4: Esterification

Esterification is the reverse of hydrolysis and leads to an equilibrium reaction, which is the

reason that quantitative esterification is possible only by continuous removal of one of

theproducts, i.e. ester or water. In the case of transesterification, an alcohol is released instead

of water. Suitable catalysts are sulphuric acid, hydrogen chloride, arylsulphonic acids such as

ptoluenesulphonic acid, and chlorosulphuric acid. Phosphoric acid, polyphosphoric acids, and

mixtures of acids are also recommended Removal of water usually involves the addition of

entrainers, which form azeotropes with relatively low boiling points and high water contents

(usually toluene, xylene.

FLOW CHART

Co-solvent

PHASE SEPARATION

Reaction water

Solvent

Entrainer

Alcohol

Acid

Alcohol

Catalyst

Entrainer

ESTERIFICATION

VOC

PRODUCT


108

NODE 5 OF 6 : EsterificationDESIGN INTENT : Esterification process operations



None. Flow. No flow. No flow ofcooling mediumto reactor.

Uncontrolledreaction.Pressurization /explosion hazard.

SOP.

Supervision.

4 3 12

More. Flow. More flowat vent.

Loss of coolingmedium atcondenser.

More flow atcondenser vent.

SOP.

Supervision.

4 3 12

Less. Flow. Less flow. Less flow ofcooling mediumto condenser.

Emission atcondenser vent.

SOP.

Supervision.

4 3 12

Reverse Flow. Reverseflow.

Reverse flow atvacuum line ifpower fails.

Disturbedoperation.

SOP.

Supervision.

3 3 9 Provide NRV in vacuumline.

As WellAs.

Composition Entrained. Removal ofwater usuallyinvolves theaddition ofentertainers,which formazeotropes withrelatively lowboiling pointsand high watercontents (usuallyToluene, Xylene,Cyclohexane.

Flammablesolvents handlingabove their flashpoint.

Fire/explosionhazard.

SOP.

Supervision.

4 3 12


109




As WellAs.

Effluent. Effluentgeneration.

Reaction watersolvent entrainedalcohol.

Effluentgeneration isgenerally low, aswater is the onlyby – product ofesterificationreactions.

Waste streams canbe reduced byrecovering (andreusing) anyorganic solvents,water and alcoholcomponents.

3 3 9

As WellAs.

Emissions. Vent gases. VOC. Emission at vent. Reflux condenser. 3 3 9

As WellAs.

Solid waste. Solid wastedisposal.

Spent catalystwhich are;



3 3 9


Static sensitivesolvents are usedas entrained.


Equipments areearthed.


More. Temperature Moretemperature

Reactionexotherm –moderate.

Emission at vent. Process control.

Supervision.

3 3 9

Less. Temperature Lesstemperature


More. Pressure. MorePressure

Excessiveheating.

Release offlammable vaporsat vent.

Process control.Supervision.

3 3 9


110




Less. Pressure. LessPressure.

Vacuum in thesystem.Fast pumpingout and ventclosed.Fast cooling,vent closed.


– – –



As WellAs.

Composition Impurities. Hydrolysisproducts.

Most esterspossess lowtoxicity becausethey are easilyhydrolysed oncontact withwater or moist air.

Process control.

Supervision.

3 3 9

More. Level. More level. Human error.Excessivecharging ofbatch


Sight glass/ glassequipment


Less. Level. Less level. Less batchcharging.

Human error.

Thermowell maynot dip.

Unsafe condition.

SOP.

Supervision.

3 3 9


111

NODE 5: HydrolysisHydrolysis involves the addition or substitution of water (H2O) into a compound. Hydrolysis

involves the reaction of an organic with water to form two or more new substances.

Hydration is the process variant where water reacts with a compound without causing its

decomposition.

Environmental issues of Hydrolysis processes;

Air: There are generally low VOC arisings from reactors

Water: In most cases, hydrolysis and hydration products are biodegradable.


112

NODE – 6 : HYDROLYSIS.DESIGN INTENT :

GUIDEWORD


S P R ACTION


Uncontrolled reaction.

Pressurization /explosion hazard.

SOP.

Supervision.

3 3 9

More. Flow. More flow atvent.


More flow at condenservent.

SOP.

Supervision.

3 3 9


Emission at condenservent.

SOP.

Supervision.

3 3 9

Reverse. Flow. Reverse flow. Reverse flow atvacuum line ifpower fails.

Disturbed operation. SOP.

Supervision.

3 3 9 Provide NRV in vacuum line.

As WellAs.

Flow. Effluentgeneration.

Mother liquor.

Washings.

Environmental issues. ETP provided. 3 3 9

As Wells.

Emissions. Vent gases. VOC.Receiver vents

Environmental issues.Health hazard due tovapors emissions atwork place.

4 4 16


113

NODE – 6 : HYDROLYSIS.DESIGN INTENT :

GUIDEWORD


S P R ACTION

Other. Flow. Static charge. Handling ofstatic sensitivematerial.

Static charge as sourceof ignition, fire hazard.

Fire explosion hazarddue to static charge inhandling of solvents.


4 4 16 Provide effective measures forprevention of accumulation of staticcharge to a dangerous extent.

More. Temperature. Moretemperature.

Reactionexotherm –mild.

Emission at vent. Reflux condenserprovided.

3 3 9

Less. Temperature. Lesstemperature.



Excessiveheating.

Release of flammablevapors at vent.

Process control.Supervision.

3 2 6





Not significant. Equipments aredesigned for vacuum.

– – –


114

NODE – 6 : HYDROLYSIS.DESIGNINTENTGUIDEWORD


S P R ACTION

As WellAs.

Composition. Impurities. By – products, Hydrolysis involvesthe reaction of an organic with waterto form two or more newsubstances.

Not significant. Process control.

Supervision.

3 3 9

More. Phase. More phases. Gas, liquid phase. Not significant. – – –More. Level. More level. Human error.

Excessive charging of batch.Entrainment, ingressof material in ventline.



Less. Level. Less level. Less batch charging.

Human error.

Thermowell may not

dip.

Unsafe condition.

SOP.

Supervision.

3 3 9

Other. Handling. Corrosive

chemicals

handling.

Handling of Sodium Hydroxide. Health hazard. 3 3 9 Provide safety shower and

eye wash fountain near

corrosive chemicals handling

area.

Other. Handling. Solid waste

generation.

Spent catalyst.

Residue.

Environmental issues. Hazardous solid

waste disposal to

CHWTSDF.

3 3 9


115

NODE 5 OF 6 : Other unit process and operationsDESIGN INTENT : Other unit process and operationsGUIDEWORD

PARAMETER

DEVIATION CAUSE

CONSEQUENCE

PROTECTIONMEASURES S P R

ACTIONSUGGESTED


Uncontrolledreaction.Pressurization /explosion hazard.

SOP.

Supervision.

4 3 12

More. Flow. More flowat vent.


More flow atcondenser vent.

SOP.

Supervision.

4 3 12


Emission atcondenser vent.

SOP.

Supervision.

4 3 12

Reverse Flow. Reverseflow.

Power failureduring recoveryof solvent byvacuumdistillation.

Ingress of air tohot flammablesolvent in thedistillationsystem.

Fire/ explosionhazard.

SOP.

Supervision.

3 3 9 Provide Nitrogen forbreaking vacuum duringsolvent recovery bydistillation.

As WellAs.

Effluent. Effluentgeneration.

Mother liquor.

Washings.


ETP provided. 3 3 9


116

NODE 5 OF 6 : Other unit process and operationsDESIGN INTENT : Other unit process and operations

Guide Word Parameter Deviation Cause ConsequenceProtectionMeasures S P R Action Suggested

As Well As. Emissions. Vent gases. VOC. Environmentalissues.

SOP.

Supervision.

3 3 9 Verify the condensercapacity so that solventloss from the systemduring reflux will beminimized.Provide temperaturecontroller for steam line athot water system.

As Well As. Solid waste. Solid wastegeneration.

Spent catalyst.

Residue.



3 3 9


Handling ofstatic sensitivematerial.




More. Temperature

Moretemperature.

Excessiveheating.

Emission at vent. TI.Supervision.

3 3 9 Provide temperaturecontroller for steam line athot water system.

Less. Temperature

Lesstemperature

Excessivecooling.



117


guideword parameter deviation cause consequence

protectionmeasures s p r action suggested

More. Pressure.Morepressure.

Excessiveheating whenlow boilingsolvent insidereactor.

Pressurization.SOP.

Supervision.4 3

12

Provide SRV on thejacket of the reactorshandling low boilingsolvents.






– – –


Gas, liquidphases.


As WellAs.

Composition Contamination

Unreacted toxicreactants

Health hazard inhandling downstream operations.

Process control.

Supervision.

3 3 9

More. Level. More level. Human error.Excessivecharging ofbatch





118




Less. Level. Less level.Less batchcharging.Human error.

Thermowell maynot dip.Unsafe condition.

SOP.

Supervision.2 2 4

Other. Handling. Powdershandling.

Safety class ofthe powderhandled notknown.

Dust explosionhazard.

SOP.

Supervision.


3 3 9 The reactions that occurwhen a solid heats andignition starts are farmore complicated thanfor a gas and may includeoxidation,decomposition, meltingand vaporisation. Theresult is that theflammability andignitability of a dust canonly be characterizedafter suitable tests. Carryout dust safety tests andutilize the data whileequipment selection andoperation .


119




Other. Handling.Hazardouschemicals

Acid fumesrelease .

Transfer ofHydrochloricAcid by vacuum.

Acidic vapors tovacuum system.Acidic effluentgeneration.

SOP.

Supervision.

3 3 9 Avoid transfer of acidssuch as HydrochloricAcid by vacuum.Consider AODP/peristaltic pump fortransfer ofHydrochloric Acid.


Hazardouschemicalsrelease

Acetone releaseas by product inprocessoperation of 3: 5DCA

Fire/explosionhazard

Supervision 4 4 16



NOx release atvent in processoperation of 3: 5DCAScrubbermalfunction

Toxic gas release SupervisionScrubber

4 4 16



Water reactivechemicals suchas phosphrouspenta chloriderelease

Decompositionwith waterreleasing toxicgasesHealth hazard

due to vapors

Supervision 4 3 12 Store chemicalsconsidering thecompatibility andreactivity hazards atstore/ warehouse.


120




emissions at workplace.Pressurization ofcontainerReactivity/compatibilityhazards in caseaccidental mix upat ware house ,drain ,equalization tankof ETP .



Water reactivechemicals suchas phosphrousOxy chloriderelease

POCL3Potentially explosivereaction withwater evolvesHydrogenChloride andPhosphine.Sufficientquantaties ofPhosphine amyignite.

4 3 12


121






Tri ethyl aminereleased into thesoil,

released into thewater,

released into theair

may leach intogroundwater, thismaterial mayevaporate to amoderate extent.may evaporate toa moderateextent. estimatedbioconcentrationfactor (BCF) ofless than 100.This material isnot expected tosignificantlybioaccumulate.

expected to bereadily degradedby reaction withphotochemicallyproducedhydroxyl radicals

this material isexpected to bereadily removedfrom theatmosphere by wetdeposition.

3 3 9


122




Sodium azideWhen releasedinto the soil,

released into theair,

released intowater

not expected tobiodegrade. expected toleach into groundwater.

When released into theair, this material may bemoderately degraded byphotolysis.

expected to be very toxicto aquatic life. TheLC50/96-hour values forfish are less than 1 mg/l.

3 3 9



Acetic anhydridereleased into thesoil,

released towater,.

expected to leach intogroundwater.

expected to react andform acetic acid.

Thismaterial isnot expectedtosignificantlybioaccumulate.

3 3 9


123






Sodium cyaniderelease

Reaction withacids

Contact withWater or weakalkalinesolutions

Exposure to CO2from air

Incompletedistruction of

Sodium cyanideis expected to bevery toxic toaquatic life.

Reacts with acidsto liberate toxicand flammablehydrogen cyanidegas.

can producedangerousamounts ofhydrogen cyanidein confined areas.Reacts with CO2in air to formhydrogen cyanidegas

releasingHydrogencyanide

Dedicated storage 5 4 20 Ensure completedistruction of sodiumcyanide in the effluentstream before mixing itto any other stream .


124




sodium cyanidein Effluentstream

gas in casecoming in contactwith acidic stream

Other. Odor Methylmercaptanrelease

Methylmercaptan isgenerated inThiaclopridprocess . being aodor neusenceany release ofthe gas should besent toincinerationfollowed byeffectivescrubbers .

odor neusence Supervision 4 4 16 Methyl mercaptanbeing a odor neusenceany release of the gasshould be sent toincineration followedby effective scrubbers .

Other Maintenance Repair overinstallation.

Inspection/maintenance.Residual gas inthe system needto be removed.

Fire/ explosion.

Health hazard.

PPE.

Work permit.

4 3 12

125

NODE 7 EFFLUENT TREATMENT PLANT

Existing Treatment Scheme for Trade Effluent

Primary treatment:

The system is designed to treat 250 m3/day of wastewater. The Effluent is collected in the

collection/equalization tank through Oil & Grease Trap, where floating oil & grease is

removed manually. The equalization tank is provided with alkali dosing & acid dosing

arrangement for pH neutralization & coarse bubble diffuser is provided to mix the

wastewater. Alum and Poly is dosed in the equalization tank itself. This effluent is pumped to

Primary Settling tank provided with Hopper bottom. Suspended and coagulated solids get

settled at the bottom of settling tank which is pumped to decanter. Filtrate from decanter is

taken back to neutralization tank and sludge is taken to sludge drying beds. Clear supernatant

will overflow into the bioreactor.

Secondary treatment:

The neutralized effluent is entering the bioreactor. In the bio reactor, dissolved organicmaterial is degraded by the micro–organisms present in the bio reactor. Oxygen required forthe oxidation of organic matter will be provided by means of proposed diffuser aerationsystem which will mix the contents of the bioreactor also. The mixed liquor will overflowinto Secondary Settling Tank (SST).In the secondary settling tank, solid-liquid separation takes place and solids i.e. biomass willsettle at the bottom of the tank. Settled biomass is recycled to the bio reactor for maintainingthe MLVSS concentration by using proposed sludge recycle pumps and excess biomass iswasted periodically to the sludge sump. The clear overflow from the Secondary Settling Tankfed to tertiary treatment.Tertiary treatment:

The system is designed to treat 250 m3/day of wastewater. The clear effluent from secondarytank shall be pumped through a pressure sand filter (PSF) for removing any fine solidsescaping the secondary Settling tank & then from Activated Carbon filter for removal ofcolor & odor. The final treated water shall be collected in the final treated water tank. Fromhere it will discharge to CETP.Sludge Dewatering

The sludge generated from the primary and secondary settling tank is pumped to sludgedrying bed. The wet sludge obtained from the sludge drying beds will be sent for disposal toCommon Hazardous Waste Treatment Storage Disposal Facility.


126

NODE : 6 of 6 : ETPDESIGN INTENT : Effluent treatmentGuideword Parameter Deviation Cause Consequence

Protectionmeasures S P R Action required

None Flow No Flow ofThe thoroughlymixed effluentto the ‘SettlingTank’

Transfer Pump’ (TP)failure / malfunctioning/ power failure

Valve failure

Delayed operation. Supervision.SG

3

3

3

3

9

9

Provide Logbook/ records.SOP and checklist for transfer.

More Flow More qty flowto ETP

Large spill in plant

Fire fighting water

Human error

Filter blockage

Over flow , spillhazard

Supervision 3 3 9

Less Flow Less qty flowto ETP

Leak over piping, valuegasket failure etc.

Spill hazard. Supervision. 3 3 9

Reverse

Flow Reverse flow Not anticipated - - -

Aswell as

Flow Spill Piping Leak corrosivechemicals

Health hazard Safety shower andeye wash fountain

3 3 9

Other Flow Static charge Not anticipated ashazard aqueous solution


2 1 2

Otherthan

Flow Other stream Not anticipated Dedicated piping 2 1 2

More Temperature Hightemperature

Not anticipated - - -


127

NODE : 6 of 6 : ETPDESIGN INTENT : Effluent treatmentGuideword Parameter Deviation Cause Consequence

Protectionmeasures S P R Action required

Less TemperatureLesstemperature


More Pressure More pressure Not anticipated Systems Open toatmosphere

- - -

Less Pressure Less pressure Vacuum not anticipated Systems Open toatmosphere

- - -

More Composition Incompitablesmix up

The effluent outflowfrom the various processtank washing and floorwashing is collected inthese tanks, throughcommon header.

Potential for seriousconsequencesdepending up on mixup (Ref. Annexure 1for compatibility).

Supervision. 4 3 12

Route the spill/floor washingthroughcollection pit forcontrolledtransfer to ETPfor treatment .

More Phase Solid waste The settled heavysludge is collectedthrough the dischargevalve into a ‘SludgeDrying Bed orCentrifuge or FilterPress’

Waste accumulationat site

Sludge will bedisposed by thirdparty (AuthorizedSolid wastemanagementcompany).

3 3 9 .

NODE : 6 of 6 : ETPDESIGN INTENT : Effluent treatmentGuide Parameter Deviation Cause Consequence Protection S P R Action required


128

word measuresAswell as

Composition Contamination water generated duringaccidental spill ,floorwashings , sprinklerwater , fire fightingwater

Unsafe condition Supervision 3 3 9 Provide suitablearrangement indrain system toavoid anyorganiccontaminatedwater generatedduring accidentalspill ,floorwashings ,sprinkler water ,fire fightingwater enteringin storm darinsystem .

More Level Higher level atHolding CumEqualizingTank

The effluent outflowfrom the various processtank washing and floorwashing is collected inthese tanks, throughcommon header.Overfilling in error

Overflow Equalization tank/NeutralizationTank

Supervisdion

3 3 9

Less Level Less level attank

Human error Transfer pumpsuction starving

Supervision 2 2 4

Other Handling Handling ofcorrosivechemicals

Acid and bases are used Injury in case ofsplash

PPESafety shower andeye wash fountain

3 3 9


129

NODE : 6 of 6 : Sub node 6.1 hazardous waste handlingDESIGN INTENT : hazardous waste handlingGuideword

Parameter Deviation Cause Consequence Protectionmeasures

S P R Actionrequired

Other Hazardouswaste

Hazardous wastegenerationduring processoperations

Cat. No. 33.3. - Sludge and filterscontaminated with oil( 1.80 MT/A)Cat. No. 35.1. -Spent catalyst( 36 MT/A)Cat. No. 5.1. -Used / spent oil( 0.6 MT/A)Cat. No. 20.3. -Spent solvents( 30 MT/A)

Hazardous wasterdisposal issues

CPCB registeredand MPCBauthorizedreprocess or /CHWTSDF forIncineration.

4 4 16



Cat. No. 34.3. -Chemical sludge from wastewater treatment( 66.6 MT/A)Cat. No. 33.2 -Sludge from treatment wastewater

Hazardous wasterdisposal issues CHWTSDF for

landfill.

4 4 16



Cat. No. 35.1. -Filters and filter materialwhich have organic liquid.( 6 MT/A)Cat. No. 10.3. -Distillation Residues ( 99MT/A)

Hazardous wasterdisposal issues CHWTSDF for

incineration.

4 4 16



Cat. No. 26.1. -Process waste sludge /Residues (300 MT/A)Cat. No. 33.3. -Discarded containers (Plastic/ PP / Rubber / Glass.) (30 MT/A)


CHWTSDF fordisposal as perwaste disposalcriteria.

4 4 16



Cat. No. 33.3. -Discarded containers /barrels / liners.


Decontaminated /puncture/cut/disposal through MPCBapproved unit.

4 4 16

130

2.9.4 COMPATABILITY/ REACTIVITY HAZARDS(Of chemicals unintended mix up)

Chemicals and Reactive Groups in this Mixture:Acetic AnhydrideHydrochloric Acid, SolutionIsopropanolN,N-DimethylformamideSodium AzideTriethylamine

--------------------------------------------------

ACETIC ANHYDRIDE mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM ---

HYDROCHLORIC ACID, SOLUTION mixed with ACETIC ANHYDRIDE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction may be particularly intense, violent, or explosiveReaction products may be explosive or sensitive to shock or frictionPOTENTIAL GASES:Carbon Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

HYDROCHLORIC ACID, SOLUTION mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM ---

ISOPROPANOL mixed with ACETIC ANHYDRIDE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)POTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

ISOPROPANOL mixed with HYDROCHLORIC ACID, SOLUTION -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)POTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

ISOPROPANOL mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM ---

131

N,N-DIMETHYLFORMAMIDE mixed with ACETIC ANHYDRIDE -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N,N-DIMETHYLFORMAMIDE mixed with HYDROCHLORIC ACID, SOLUTION -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction products may be toxicPOTENTIAL GASES:AmmoniaCarbon Monoxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N,N-DIMETHYLFORMAMIDE mixed with ISOPROPANOL -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N,N-DIMETHYLFORMAMIDE mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM ---

SODIUM AZIDE mixed with ACETIC ANHYDRIDE -PREDICTED HAZARDS:Reaction may be particularly intense, violent, or explosivePOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

SODIUM AZIDE mixed with HYDROCHLORIC ACID, SOLUTION -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction products may be explosive or sensitive to shock or frictionReaction products may be flammableReaction products may be toxicPOTENTIAL GASES:AmmoniaHydrazoic AcidNitrogen--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

132

SODIUM AZIDE mixed with ISOPROPANOL -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction products may be toxicPOTENTIAL GASES:Hydrogen HalideNitrogen--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

SODIUM AZIDE mixed with N,N-DIMETHYLFORMAMIDE -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

SODIUM AZIDE mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM ---

TRIETHYLAMINE mixed with ACETIC ANHYDRIDE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction may be particularly intense, violent, or explosivePOTENTIAL GASES:Carbon Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

TRIETHYLAMINE mixed with HYDROCHLORIC ACID, SOLUTION -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction may be particularly intense, violent, or explosiveReaction products may be corrosiveReaction products may be toxicPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

TRIETHYLAMINE mixed with ISOPROPANOL -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

TRIETHYLAMINE mixed with N,N-DIMETHYLFORMAMIDE -PREDICTED HAZARDS:

133

Reaction liberates gaseous products and may cause pressurizationReaction products may be flammableReaction products may be toxicPOTENTIAL GASES:AmmoniaHydrogen Sulfide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

TRIETHYLAMINE mixed with SODIUM AZIDE -PREDICTED HAZARDS:Reaction may be particularly intense, violent, or explosivePOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

TRIETHYLAMINE mixed with itself -INTRINSIC REACTIVE HAZARDS:No reaction expected.--- END OF HAZARDS FOR THIS ITEM --- ---

134

SECTION 3: FAILURE FREQUENCY ANALYSIS

3.1 FAILURE FREQUENCY

The frequency assessment stage of the analysis involved defining the potential release

sources and subsequently determining the likelihood (frequency) of the various

releases. The failure frequencies were determined using failure item counts for each

of the failure items identified and publicly available historical failure rate data.

Ignition probability data was used to estimate the probability of a release subsequently

being ignited.

3.1.1 Flange gasket failure/ gland failure. An accident/ event for gasket leakage/

failure can be termed as “quite probable”. The hole size in a gasket failure

may be that due to complete section between bolt holes or something much

smaller. The hole size for a complete section failure of a gasket is usually

calculated.

3.1.2 Failure of transfer line. The possible route of hazardous material going out of

containment in open atmosphere is the rupture of a transfer line. The case of

guillotine type failure of tanker unloading hose / transfer line or bottom nozzle

undergoing guillotine type of failure also are rather low. Failure frequency as

per published literature for such lines is low and such events can be

considered, “foreseeable”.

3.1.3 Accidental spill of flammable solvent and uncontrolled spreading pool

followed by fire is considered as Worst Possible Scenario. It is to be noted that

loss caused due to this event is very high but the probability is low; however,

in case of neglect of maintenance or natural calamities such as earthquake the

possibility exists. Such events are unlikely to happen and are not credible.

Failure frequency of catastrophic rupture of such pressure vessel is very low

i.e. 3 per million per year.

135

3.2 EVENT TREE ANALYSIS

HYDROGEN GAS RELEASE

Fire/ Explosion frequency = 0.004 + 0.0004 = 0.0044, R = 0.9936, MTBF, 155 yrs.*0.5 if distance to 50 % LFL falls within plant (with control of company) and

HYDROGEN GAS RELEASE

P = 0.0008 + 0.00072 = 0.00152, R = 0.99848, MTBF 657 yrs.0.1 if distance to 50 % LFL falls inside electrically classified area.

136

FLAMMABLE SOLVENT RELEASE

Pool fire frequency = 0.0001*0.1 if distance to 50 % LFL falls inside electrically classified area.

137

SECTION 4: CONSEQUENCE ANALYSIS

4.1INTRODUCTION

4.1.1 LIKELY ACCIDENT SCENARIOS

TABLE NO. 4.1: LIKELY ACCIDENT SCENARIOS.

1 Bromine2 Hydrogen3 Toluene

These accident scenarios are divided in two categories considering the consequence

seriousness and occurrence frequency.

MAXIMUM CREDIBLE LOSS SCENARIO (MCLS).

WORST POSSIBLE SCENARIO.

4.1.2 MAXIMUM CREDIBLE LOSS SCENARIO (MCLS)

Maximum Credible Loss Scenario (MCLS) is one of the methodologies

evolved to access the events in realistic and practical way. An MCLS can be

described as the worst “credible” accident or as an accident with a maximum

damage distance, which is still believed to be probable. The analysis, however,

does not include a quantification of the probability of occurrence of an

accident.

The MCLS aims at identifying undesirable and hazardous events causing the

Maximum damage to human beings environment around the industry under

the consideration.

Leak from hose/ piping failure are quite probable events. Such accidental

release is considered as MCLS.

4.1.3 WORST POSSIBLE SCENARIO

Worst Case Scenario/ MCA (Maximum Credible Accident) Accident Scenario

accidental release of Bromine tank failure is considered as Worst Case

Scenario/ MCA (Maximum Credible Accident).

138

4.2 CONSEQUENCE ANALYSIS

ACCIDENT SCENARIO NO. 7 : ACCIDENTAL RELEASE OF BROMINE

CHEMICAL NAME: BROMINE CAS. 7726-95-6Mole Weight 78.50 g/mol Ambient B.P. 58.6 oC VP. at ambient temp 0.35 atmERPG -1 0.1 ppm ERPG -2 0.5 ppm ERPG -3 5 ppmIDLH 3 ppmAmbient Saturation Concentration: 347,206 ppm or 34.7%SOURCE STRENGTH : evaporating Pool dia. 4 m, 1.5 F

ACCIDENT SCENARIO NO. 7.1

HREAT MODELEDTOXIC AREA OF VAPOR CLOUD

ERPG IDLH

THREAT ZONE

Red ERPG -3 5 ppm 803 mOrange ERPG -2 0.5 ppm. 3.4 kmYellow ERPG -1 0.1 ppm. 8 km

IDLH 3 ppm 1.1 km

THREAT AT POINT:

139

Model Run: Gaussian

THREAT MODELED: TOXIC AREA OF VAPOR CLOUD

THREAT ZONE

Red ERPG -3 5 ppm. 32 meters.

Orange ERPG -2 0.5 ppm. 104 meters.

Yellow ERPG -1 0.1 ppm. 244 meters.

140

ACCIDENT SCENARIO NO. 6: ACCIDENTAL RELEASE OF HYDROGEN

CHEMICAL NAME: HYDROGEN.

Mole Weight 2.02 g/mol Ambient B.P. - 252.8 oC VP. at ambient temp > 1 atm.TEEL-1 145000 ppm TEEL -2 280000 ppm TEEL -3 500000ppmLEL 40000 ppm UEL 75000 ppmAmbient Saturation Concentration: 1,000,000 ppm or 100.0 %.

ACCIDENT SCENARIO NO. 6.1 (MCLS)Hydrogen gas escaping from pipe (not burning), through pipe.

THREAT MODELED: FLAMMABLE AREA OF VAPOR CLOUD


Red 24,000 ppm = 60% LEL = Flame Pockets. 30 meters.

Yellow 4,000 ppm = 10% LEL. 73 meters.

ACCIDENT SCENARIO NO. 6.2 (MCLS)THREAT MODELED: OVER PRESSURE (BLAST FORCE), VCE

141

OVER PRESSURE (BLAST FORCE), VCE

Red. 8.0 psi: Destruction of buildings. 24 meters.

Orange. 3.5 psi: Serious injury likely. 27 meters.

Yellow. 1.0 psi: Shatters glass. 45 meters.

ACCIDENT SCENARIO NO. 6.3Flammable gas is burning as it escapes from pipe.

THREAT MODELED : JET FIRE MODEL

S. N. THERMAL RADIATION LEVEL EFFECT DISTANCE

1. Distance to 10.0 KW/m2 (potentially lethal within 60 sec). < 10 meters.

2. Distance to 05.0 KW/m2 (2nd degree burns within 60 sec). < 10 meters.

3. Distance to 02.0 KW/m2 (pain within 60 sec). < 10 meters.

ACCIDENT SCENARIO NO. 6.4 (MCA).

Hydrogen cylinder rupture (involved in fire).

THREAT MODELED: FIRE BALL MODEL

142

S. N. THERMAL RADIATION LEVEL EFFECT DISTANCE

1. Distance to 10.0 KW/m2 (potentially lethal within 60 sec). 18 meter.

2. Distance to 05.0 KW/m2 (2nd degree burns within 60 sec). 25 meter.

3. Distance to 02.0 KW/m2 (pain within 60 sec). 38 meter.

Worst possible accident : hydrogen trolley

Catastrophic failure for 40 kg containment

Thermal radiation 5 .8 Kw/m2 , corresponding to 1% fetality

Affect distance 70 m

Exposure for 90 second

The graph in PHAST , 1.5 F enclosed

144

4.6 ACCIDENT SCENARIO NO. 5: ACCIDENTAL SPILL OF TOLUENE.

CHEMICAL NAME: TOLUENE.

Mole Weight 92.14 g/mol Ambient B.P. 110.5 oC VP. at ambient temp 0.048 atmERPG-1 50 ppm ERPG -2 300 ppm ERPG -3 1000 ppmIDLH 500 ppm LEL 12000 ppm UEL 71000 ppmAmbient Saturation Concentration: 48,470 ppm or 4.85%.

SOURCE STRENGTH

Evaporating Puddle of Puddle Area: 1 square meter.

Model Run: Gaussian

ACCIDENT SCENARIO NO. 5.1THREAT ZONE

Red ERPG -3 1000 ppm. < 10 meters.Orange ERPG -2 300 ppm. < 10 meters.Yellow ERPG -1 50 ppm. < 10 meters.

IDLH 2000 ppm. < 10 meters.

145



THREAT ZONE

Red 6600 ppm = 60% LEL = Flame Pockets. < 10 meters.Yellow 1100 ppm = 10% LEL. < 10 meters.


THREAT MODELED: OVER PRESSURE (BLAST FORCE)

VAPOR CLOUD EXPLOSION

No explosion: no part of the cloud is above the LEL at any time.

ACCIDENT SCENARIO NO. 5.4THREAT MODELED: THERMAL RADIATION FROM POOL FIRE.

S. N. THERMAL RADIATION LEVEL EFFECT DISTANCE1. Distance to 10.0 KW/sq.m (potentially lethal within 60 sec). < 10 meters.2. Distance to 5.0 KW/sq.m (2nd degree burns within 60 sec). < 10 meters.3. Distance to 2.0 KW/sq.m (pain within 60 sec). < 10 meters.


THERMAL RADIATION FROM POOL FIRE.

FIGURE NO. 4.1: THERMAL RADIATION FROM POOL FIRE.

146

S. N. THERMAL RADIATION LEVEL EFFECT DISTANCE1. Distance to 10.0 KW/sq.m (potentially lethal within 60 sec). 10 meters.2. Distance to 5.0 KW/sq.m (2nd degree burns within 60 sec). 13 meters.3. Distance to 2.0 KW/sq.m (pain within 60 sec). 17 meters.4. Distance to 4.0 KW/sq.m (Emergency Action). 13.5 meters.

ACCIDENT SCENARIO NO. 4: ACCIDENTAL SPILL OF FURNACE OIL

Continuous release of Furnace Oil due to failure a pipe line having diameters of 40 mm at

storage tank in dyke.

THREAT MODELED: THERMAL RADIATION FROM POOL FIRE.

SR. NO. THERMAL RADIATION LEVEL EFFECT DISTANCE

1 10.0 KW/M2 (potentially lethal within 60 sec.). 9 meters.

2 5.0 KW/M2 (2nd degree burns within 60 sec.). 13 meters.

3 2.0 KW/M2 (pain within 60 sec.). 18 meters.

ACCIDENT SCENARIO NO. 5: ACCIDENTAL RELEASE OF HYDROCHLORIC ACID

CHEMICAL NAME: HYDROCHLORIC ACID 35%(by weight)Mole Weight 36.46 g/mol Ambient B.P. 62.9 oC VP. at ambient temp 0.17 atmERPG-1 3 ppm ERPG -2 20 ppm ERPG -3 150 ppmIDLH 50 ppm PEL 5 ppm - UEL -Ambient Saturation Concentration: 173,615 ppm or 17.4%Max Average Sustained Release Rate: 10.1 grams/min, (averaged over a minute or more)

ACCIDENT SCENARIO .1: (MCA)Hydrogen Chloride gas escaping from scrubber vent.

THREAT MODELED:

TOXIC AREA OF VAPOR CLOUD

TOXIC AREA OF VAPOR CLOUD.

THREAT ZONE

1. ERPG – 3 (150 ppm) : Red. 16 meters.

2. ERPG – 2 (20 ppm) : Orange. 44 meters.

3. ERPG – 1 (3 ppm) : Yellow. 115 meters.

147

NOTE:

1. ATMOSPHERIC DATA

Wind from West at 4meters m/s

Stability Class D Cloud cover 5 tenth

No Inversion Relative Humidity 50 % Air temperature 30 oC

2. Consequences zones have been calculated using software ALOHA and also software based on the “TNO Yellow Book”.Method for calculation of the Physical Effects of the escape of Dangerous Material (Liquid & Gases) Published by theDirectorate General of Labour, Ministry of Social Affair, Netherlands(1979).

3. Apart from the maximum credible releases, the conservative approach appears in adoption of atmospheric conditions, usedin the dispersion calculation. In general, the assumptions/ conditions will result in the largest damage distances. Hence, itmust be remembered that this analysis will be pessimistic & conservative in approach & is only a planning tool. Its useshould not be extended without understanding its limitations.

4. DISCLAIMER:

Information contained in this report is believed to be reliable but no representation, guarantee or warranties of any kind aremade as to its accuracy, suitability for a particular application or results to be obtained from them. It is up to themanufacturer to ensure that the information contained in the report is relevant to the product manufactured/ handled orsold by him as the case may be. We make no warranties expressed or implied in respect of the adequacy of this documentfor any particular purpose.

148

SECTION 5: IMPACT ASSESSMENT

Effect models are used for the impact analysis. These models used to determine how people

are injured by exposure to heat, overpressure and toxic load. Effect models make use of a

probit function. In probit function a link exists between the load and percentage of people

exposed who suffer particular type of injury.

5.1 THERMAL RADIATION IMPACT

The effect of human exposure to a fire is a function of both the intensity of heat

radiation and the duration of exposure. The harmful effect can be characterized by a

thermal dose that is defined by the function

3

4It .

Where,

Y = probit value,I = heat radiation intensity, andt = exposure duration.

The probit equation utilized is the Eisenberg equation.

3

4

ln56.29.14 ItY

A probit function has been used to evaluate the likelihood of fatality for different heat

flux exposures.

A radiation level of 12.5 KW/m2 will give 1 % fatalities for short exposure periods of

30 seconds and 50 % fatalities for exposures of over 80 seconds.

TABLE NO. 5.1: FATAL THERMAL RADIATION EXPOSURE LEVELS.

RADIATION LEVELKW/m2

SECONDS EXPOSURE FOR A % FATALITY LEVELS

1 % 50 % 99 %

1.6 500 1300 3200

4.0 150 370 930

12.5 30 80 200

37.5 8 20 50

149

TABLE NO. 5.2: EFFECTS OF THERMAL RADIATION ON UNPROTECTED SKIN.

RADIATION LEVEL(KW/m2)

DURATION PERIOD SECONDS BEFOREPain is Felt Blistering Starts

22 02.0 03.018 02.5 04.311 05.0 08.508 08.0 13.505 16.0 25.02.5 40.0 65.0

Below 2.5 Prolonged exposure can. be tolerated.

Continued exposure to heat flux of 4.0 KW/m2 is considered sufficient to cause

injury. Hence, injury risk was assessed based on exposure to this level of heat flux or

greater. It is estimated that heat flux of 10.0 KW/m2 is likely up to 9 m distance from

the centre of the fire. It is assumed that any person near fire can take shelter within 90

seconds.

5.2 OVER PRESSURE IMPACT

TABLE NO. 5.3: EFFECT OF BLAST PRESSURE WAVE.

OVER PRESSURE (bar) EFFECTS0.01 Shattering of glass windows. Failure of panels.

0.03 Shattering of asbestos siding.

0.1 Collapse of steel framing panels.

0.3 Shearing of brick walls (8-12 inches).

5.2.1 Lung Hemorrhage

or PP ln91.677

Where,

Po is the Peak Over Pressure (Pa).

= 5.1 corresponds to 54 %.

5.2.2 Ear Drum Rupture

or PP ln93.16.15

Where,



150

5.2.3 Fatality Due To Impact

or PP ln82.41.46

Where,



5.2.4 However over pressure of 3.5 psi zone at tank farm persons are likely to take

safe shelter quickly avoiding any fatality .

5.3 TOXICITY IMPACT

5.3.1 BROMINE

Human Health Effects of Bromine Vapor At Various Concentrations

ppm EFFECT

0.006 Irritation of eyes.

0.2 – 0.5 Irritation of eyes, nose and throat; cough, headache.

> 0.5 Intolerable.

40-60 Toxic pneumonitis and pulmonary oedema.

1000 Fetal within a few minutes.

5.3.3 SODIUM CYANIDE

Potential Health Effects

In most cases, cyanide poisoning causes a deceptively healthy pink to red skin color.However, if a physical injury or lack of oxygen is involved, the skin color may bebluish. Reddening of the eyes and pupil dilation are symptoms of cyanide poisoning.Cyanosis (blue discoloration of the skin) tends to be associated with severe cyanidepoisonings .

Inhalation:

Corrosive to the respiratory tract. The substance inhibits cellular respiration and maycause blood, central nervous system, and thyroid changes. May cause headache,weakness, dizziness, labored breathing nausea and vomiting, which can be followedby weak and irregular heart beat, unconsciousness, convulsions, coma and death.

151

Ingestion:

Highly Toxic! Corrosive to the gastro-intestinal tract with burning in the mouth andesophagus, and abdominal pain. Larger doses may produce sudden loss ofconsciousness and prompt death from respiratory arrest. Smaller but still lethal dosesmay prolong the illness for one or more hours. Bitter almonds odor may be noted onthe breath or vomitus. Other symptoms may be similar to those noted for inhalationexposure .

Skin Contact:Corrosive. May cause severe pain and skin burns. Solutions are corrosive to the skinand eyes, and may cause deep ulcers which heal slowly. May be absorbed through theskin, with symptoms similar to those noted for inhalation.

Eye Contact:

Corrosive. Symptoms may include redness, pain, blurred vision, and eye damage.

Chronic Exposure:

Prolonged or repeated skin exposure may cause a "cyanide" rash and nasal sores.Aggravation of Pre-existing Conditions: Workers using cyanides should have apreplacement and periodic medical exam. Those with history of central nervoussystem, thyroid, skin, heart or lung diseases may be more susceptible to the effects ofthis substance .

152

SECTION 6: RISK ESTIMATION

6.1 INDIVIDUAL RISK ISOPLETH

6.1.1 Individual risk is defined by AIChE/ CCPS as risk to a person in the vicinity

of a hazard. This includes the nature of the injury to the individual, the

likelihood of the injury occurring and the time period over which the injury

might occur. Individual risk can be estimated for the most exposed individual,

for groups of individuals at particular places or for an average individual in an

effect zone. For a given incident or set of incidents, these individual risk

measures have different values.

6.1.2 Individual Risk due to incidence ‘I’ at a geographical location x, y is given as;

iyxyx IR

NIR ,,,

1

Where,

N is number of persons in the affect zone.

Continued exposure to heat flux of 4.0 KW/m2 is considered sufficient to

cause injury. Hence, injury risk was assessed based on exposure to this level

of heat flux or greater.

6.1.3 RISK ISOPLETH

Average individual risk (exposed hours/worked hours) individual risk of

fatality at Assembly point is estimated as 1.16 10-6. A broadly acceptable

level of individual risk as per the ALARP (As low as reasonably practicable)

concept of HSE, UK 10-6/year.

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6.2 SOCIETAL RISK (F-N CURVE)

Societal risk criteria are generally presented as curves on F – N plots. Mathematically,

the equation for an F – N criterion curve may be presented as; [Ball 19981].

aNkF Where,

F = the cumulative frequency of N or more fatalities.N = the number of fatalities.a = aversion factor (often between 1 and 2).k = constant.

The slope of the societal risk criterion (when plotted on a log – log basis) is equal to‘–a’ and represents the degree of aversion to multi-fatality events embodied in thecriterion.

When the F – N curve slope is equal to -1, the risk criterion is termed ‘risk neutral’. Arisk criterion for which the curve slope is more negative than -1 is said to be more riskaverse.

An anchor point along the curve (e.g. N=10 fatalities, F=10-3/year) and a slope (e.g. -1) is usually enough information to plot a risk criterion F – N curve. If any portion ofthe calculated F – N curve exceeds the criterion line, the societal risk is said to exceedthat risk criterion.In the present case any fatality unlikely in the surroundings and there is no situationpoint above the criterion line indicating insignificant societal risk.

Refer Figure section 1. 16 for : F-N Curve

SECTION 7: RISK MITIGATION MEASURES

Refer Section 1.14

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ANNEXURE 1: GLOSSARY

Acceptance Criteria(Risk).

: Defines the level of risk to which an individual is exposed, as either tolerable (negligible risk), intolerableor within the ALARP region.

Consequence : This is the severity associated with an event in terms of toxic doses, fire or explosion etc., i.e. thepotential effects of a hazardous event.

ERPG : The Emergency Response Planning Guidelines.ERPG 1: The maximum airborne concentration below which it is believed that nearly all individuals couldbe exposed for up to 1 hour without experiencing other than mild transient adverse health effects orperceiving a clearly defined, objectionable odor.ERPG 2: The maximum airborne concentration below which it is believed that nearly all individuals couldbe exposed for up to 1 hour without experiencing or developing irreversible or other serious healtheffects or symptoms which could impair an individual's ability to take protective action.ERPG 3: The maximum airborne concentration below which it is believed that nearly all individuals couldbe exposed for up to 1 hour without experiencing or developing life-threatening health effects.

Frequency : This is the number of occurrences of an event expressed per unit time. It is usually expressed as thelikelihood of an event occurring within one year.

Hazard : A physical situation with the potential for human injury, damage to property, damage to the environmentor some combination of these.

Hazardous Scenario : The identified isolatable sections and/or those which have been broken down into scenarios for specificitems of equipment.

IDLH : Immediately Dangerous To Life And Health.The maximum concentration would not cause any escape imparting symptoms or irreversible healtheffects to a person exposed for 30 minutes.

Individual Risk : The frequency at which an individual may be expected to sustain a given level of harm from therealization of specified hazards.

Individual RiskContours.

: As IR (Individual Risk) is calculated at a point, calculating the IR at many points allows the plotting of IRcontours, these being lines that indicate constant levels of risk. Most commonly used are the 1 chanceper million-year contour and the 10 chances per million-year contour.

Individual RiskOf Fatality.

: Individual risk with “harm” measured in terms of fatality. It is calculated at a particular point for astationary, unprotected person for 24 hours per day, 365 days per year. Normally measured in chancesof fatality per million years.

Individual RiskOf Injury.

: Similar to individual risk of fatality, however with “harm” measured in terms of injury.

Isolatable Section. : A system of pipes or vessels containing the hazardous materials that are bounded by specific isolation

155

points.

Isolation Point. : A point in the process, which can be used to isolate one part of the process from the rest of the system.

LEL. : Lower Flammability Limit.Expressed as % by volume of flammable gas in air. This is the minimum concentration of gas in airmixture which can ignite. Gas air mixtures below this concentration do not ignite.

Probability. : The expression for the likelihood of an occurrence of an event or an event sequence or the likelihood ofthe success or failure of an event on test or demand. By definition, probability must be expressed as anumber between 0 and 1.

QuantitativeRisk Assessment.

: A risk assessment undertaken by combining quantitative evaluations of event frequency andconsequence.

Risk. : The combination of frequency and consequences, the chance of an event happening that can causespecific consequences.

Risk Reduction. : The process of risk assessment coupled to a systematic consideration of potential control measures anda judgment on whether they are reasonably practicable to implement.

TEEL : Temporary Emergency Exposure Limits.TEEL-1: Maximum concentration in air below which it is believed nearly all individuals could be exposedwithout experiencing other than mild transient health effects or perceiving a clearly definedobjectionable odor.

TEEL-2: Maximum concentration in air below which it is believed nearly all individuals could be exposedwithout experiencing or developing irreversible or other serious health effects or symptoms that couldimpair their abilities to take protective action.

TEEL-3: Maximum concentration in air below which it is believed nearly all individuals could be exposedwithout experiencing or developing life-threatening health effects.

UFL : Upper Flammability Limit.Expressed as % by volume of flammable gas in air. This is the maximum concentration of gas in airmixture which can ignite. Gas air mixtures above this concentration do not ignite.

Vapor Cloud Explosion : An accidental release of flammable liquid or gas, there is possibility that it may form a cloud which canspread along the wind direction. Delayed ignition of the cloud away from the source of release results inVapor cloud explosion (flash back) and associated blast/ over pressure effects.

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ANNEXURE 2: ABBREVIATIONS

AIChE. American Institute Of Chemical Engineers.

ALARP. As Low As Reasonably Practicable.

BTU. British Thermal Unit.

CCPS. Centre For Chemical Process Safety.

DMP. Disaster Management Plan

ECC. Emergency Control Centre.

EIA. Environmental Impact Assessment.

EMP. Environment Management Plan.

F & E I. Fire And Explosion Index.

HAZOP. Hazard Operability.

HSD. High Speed Diesel.

IDLH. Immediately Dangerous To Life And Health.

IPL. Independent Protection Layer.

KCal. Kilocalories.

lb. Pound.

LOC. Level Of Concentration.

LOPA. Layers Of Protection Analysis.

MCA. Maximum Credible Accident.

MF. Material Factor.

MIDC. Maharashtra Industrial Development Corporation.

MoEF. Ministry Of Environment And Forests.

MSDS. Material Safety Data Sheet.

MT. Metric Ton.

NFPA. National Fire Protection Association.

PFD. Probability Of Failure On Demand.

PHA. Preliminary Hazard Analysis.

QRA. Quantative Risk Assessment.

RH. Risk Assessment And Hazard Management.

SIF. Safety Integrated Function.

TEEL. Temporary Emergency Exposure Limits.

UK. United Kingdom.

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ANNEXURE 3: REFERENCES1. Technical EIA Guidance Manual for “Pesticide Industry And Pesticide

Specific Intermediates, 2010” prepared by the Ministry of Environment

and Forests Government of India.

2. MOND INDEX Manual 1993.

3. “TNO Yellow Book”. Method for calculation of the Physical Effects of

the escape of Dangerous Material (Liquid & Gases) Published by the

Directorate General of Labour, Ministry of Social affair, Netherlands

(1979).

4. Frank P. Lees – Loss Prevention in the Process Industries – Volume I.

5. Risk Assessment for Process Industries, Loss Prevention News April -

June 2001.

6. Techniques for assessing Industrial Hazards (World Bank Technical

Paper, ISSN 0253; No. 55).

7. Ref. Table 3.8 – Vapor Pressure of Organic Compounds, R. H. Perry,

C.C., Chemical Engineers Handbook, 5th Edition (1969) McGrow – Hill

Book co. (New York, London).

8. Guideline for Quantitative Risk Assessment “Purple Book”.

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