risk assessment -...

RISK ASSESSMENT(QRA)

Proposed expansion project of Manufacturing ofchemical intermediates

At

INNOVASSYNTH TECHNOLOGIES (I) PVTLTD.

S.No. 9-24, Wasarang 34-36 , KhopoliDist.:- Raigad, Maharashtra ,

India.

JUNE 2017

2

CONTENTS

SECTION DESCRIPTION PAGE NO.

1 Introduction 03

2 Hazard identification 11

3 Consequence analysis 65

4 Impact assessment. 71

5 Failure frequency analysis. 74

6 Risk estimation 77

7 Risk mitigation measures. 78

LIST OF ANNEXURESr.no. DESCRIPTION PAGE NO.

Annexure 1 Compatibility/ reactivity hazard worksheet 80

Annexure 2 MOND index assessment worksheets 87

Annexure 3 DOW F & E index worksheets 99

Annexure 4 Preliminary hazard analysis ( project life concept ) 103

Annexure 5 Glossary. 105

Annexure 6 Abbrivations. 107

Annexure 7 References. 108

Annexure 8 DMP (onsite and off site ) Enclosed

3

SECTION 1: INTRODUCTION

1 THE ASSIGNMENT

1.1 Innovassynth Technologies (I) Pvt Ltd. is located at S.No. 9-24, Wasarang 34-

36 , Khopoli District Raigad, Maharashtra , India. The company proposed

Expansion of existing Manufacturing capacity 100 mt/m to 350 Mt/m.

Proposed project falls under the schedule of Activities - 5(f) titled manufacture

of synthetic Organic chemicals, under category “A” as per schedule in EIA

notification, 2006 and its subsequent amendments.

1.2 M/s. Goldfinch Engineering Systems Private Limited, Thane is preparing EIAreport for the proposal . Mr. Subhash Bonde of M/s. Bonde Technical Services,Thane is “Functional Area Expert – RH (Risk Assessment and HazardManagement )” enpaneled with M/s. Goldfinch Engineering Systems PrivateLimited, Thane undertook this QRA study towards compliance of TORrequirements of EIA report .

1.3 The scope of the report covers the proposed site activities of manufacturing.The battery limits of this study are restricted to the installations indicated overthe site plan.

1.4 Methodology followed in preparation of this report is as per Technical EIAGuidance Manual for Synthetic Organic Chemicals, prepared for the Ministryof Environment and Forests Government of India.

1.5 The proposed product mix involves consideration of total 119 number ofproducts . These products are Grouped under eight Groups considering unitprocesses and operations .

TABLE NO. 1.1: The proposalSr. Ref Plant Capacity Mt/MNo. Product name No. Plant Existing + addition

- DecreaseFinal

1 Friedel-crafts Reaction 75.0000 +100.0000 175.00001.1 Substituted Triazine Derivative 17 MPP 50.0000 +25.0000 75.00001.2 TINUVIN -400 68 Block 1 20.0000 + 20.0000 40.0000

Block 2 + 20.0000 20.0000Block3 + 20.0000 20.0000Block 6 + 20.0000 20.0000

2 ACYLATION - +89.2370 89.23702.1 2,4Dihydroxy 88 Block 2 +25.0000 25.0000

Benzophenone Block 3 +25.0000 25.0000Block 6 +39.2370 39.2370

4

Sr. Ref Plant Capacity Mt/MNo. Product name No. Plant Existing + addition

- DecreaseFinal

3 CONDENSATION 7.7152 25.3320 33.04723.1 5'-DMT-C-Ethyl N-Protected

Nucleoside & Phosphoramidite

60 PP-1 0.0100 +0.0204 0.0304

3.2 Ena -Protected Nucleoside &Phosphoramidite

62 PP-1 0.0100 -0.0090 0.0010

3.3 TAC Protected Necleeoside &Phosphoramidite

64 PP-1 0.0100 +0.0400 0.0500

3.4 5’-ODMT-Deoxynucleosides,Phosphoramidites andSuccinate Salts

77 PP-1 +0.2000 0.2000

3.5 DMT-LNA-Nucleosides &Phosphoramidites

78 PP-1 +0.1000 0.1000

3.6 Galnac Acyclic Succinate 79 PP-1 +0.0028 0.00283.7 UNA Phosphoramidites &

Derivatives108 PP-1 +0.0400 0.0400

3.8 Morpholino Phosphoramidites& Derivatives

109 PP-1 +0.1000 0.1000

3.9 Chiral Phosphoramidites &Derivatives

110 PP-1 +0.1000 0.1000

3.10 Bis TAc dG 112 PP-1 +0.0840 0.08403.11 5'-Biotin Phosphoramidite 114 PP-1 +0.0010 0.00103.12 5'-DMT-2'-OTBDMS-RNA

Phosphoramide AndDerivatives

48 PP-1 0.0042 +0.3958 0.4000

3.13 2-6 Diamino-9-(b-D-Ribo)Purine (DAP)

26 PP-2 0.0500 -0.0450 0.0050

3.14 N2 Phenyl Acetyl Guanosine 37 PP-2 0.0416 -0.0376 0.00403.15 2’ – Fu Amidite 5’-0-(4,4’-

Dimethoxy Trityl)-2’-FluoroUridine-3’-[(2-Cyanoethyl)-(N,N-Di Isopropyl)]-Phosphoramidite

47 PP-2 0.002 0.002

3.16 5'-Dmt-2'-Moe ProtectedNucleoside &Phosphoramidite

65 PP-2 0.0200 +0.3800 0.4000

3.17 5'-Dmt-2'-O-Methyl ProtectedNucleoside &Phosphoramidities

66 PP-2 0.0100 +0.1900 0.2000

3.18 Isosulfan Blue (2,5–Disulfophenyl Isomer)

2 PP-8 0.0084 +0.0016 0.0100

3.19 Cyclopropyl Methyl Bromide(CMB)

9 PP-3/4/50.0042

+0.3958 0.4000

3.20 Ethyl 2-Methyl-4-Pentenoate(EMPE)

18 PP-3/4/50.0833

-0.0750 0.0083

3.21 5-Bromo-Indole 21 PP-3/4/5 0.3330 -0.3030 0.0300

5


- DecreaseFinal

3.22 4-Pentenoic Acid 22 PP-8 0.8333 +1.1667 2.00003.23 Methyl Tiglate 23 PP-3/4/5 0.0166 0.01663.24 p-Nitro Phenyl Phosphate –

Disodium Salt Hexahydrate42 PP-3/4/5

0.0833+0.1167 0.2000

3.25 p-Nitro Phenyl Phosphate –Ditris Salt

43 PP-3/4/50.0833

-0.0733 0.0100

3.26 Sodium Beta GlyceroPhosphate

52 PP-3/4/51.6600

-0.6600 1.0000

3.27 1-Cyano Cyclobutane-1,2-Dicarboxylic Acid DimethylEaster / Transdiacid

58 PP-3/4/5 0.2000 +0.2000 0.2000

3.28 E-Tetracetate 63 PP-3/4/5 0.0500 +0.1500 0.20003.29 DL –Lactide 83 PP-3/4/5 +0.0083 0.00833.30 4,5-Dichloro pthalic acid 91 PP-3/4/5 +0.0083 0.00833.31 6-Bromo-Iso-indolin-1-one 93 PP-3/4/5 +0.0083 0.00833.32 Trans aconiticAcid 94 PP-3/4/5 +0.0083 0.00833.33 3,5-Bis(2-Cyanoprop-2-

yl)benzyl bromide Anastrazole intermediate

101 PP-3/4/5 +0.0083 0.0083

3.34 3,5-Bis(2-Cyanoprop-2-yl)Toluene Anastrazoleintermediate

102 PP-3/4/5 +0.0083 0.0083

3.35 2,2'-Azobis(2-methylpropionamidine)dihydrochloride

103 PP-3/4/5 +0.0100 0.0100

3.36 Ethyl-2,2-difluoro propionate 119 PP-3/4/5 +0.0416 0.04163.37 Ethyl-4-Pentenoate 19 PP-3/4/5 0.0833 0.0833

Block 3 +0.0750 4.1663.38 4-Aminobenzonitrile 81 Block 3 +0.1660 0.16603.39 P-Anisyl Propanal 75 PP-6 +4.0000 4.00003.40 4–Fluoro Isoquinoline 1 R &D Lab 0.0084 -0.0034 0.00503.41 Ethyl-2-Methyl 3-4-

Pentadienoate (EMPD)24 R &D Lab 0.5000 -0.4990 0.0010

3.42 N-Benzoyl – 3 – Tritylamino5 Phosphoramidite 2 – deoxyAdenosine (dA)

30 R &D Lab 0.0040 +0.0035 0.0005

3.43 3-Tritylamino 5-Phosphoramidite N-Bz-Dc

31 R &D Lab 0.0040 +0.0035 0.0005

3.44 N- Isobutyryl - 3- Tritylamino 5 – Phosphoramidite 2– deoxy Guanosine (dG)

32 R &D Lab 0.0040 +0.0035 0.0005

3.45 3- Tritylamino 5 – Phosphoramidite Thymidine (dT)

33 R &D Lab 0.0040 +0.0035 0.0005

3.46 5-Iodo dC 115 R &D Lab +0.0008 0.00083.47 2'-Fluoro-GiBu-3'-CEPA 116 R &D Lab +0.0008 0.0008

6


- DecreaseFinal

3.48 5'-ODMT-N6-Bz-2'-FluoroAdenosine-3'-OCEPA

117 R &D Lab +0.0008 0.0008

3.49 4-(methylamino)pentan-2-oldibenzoate (AB)

97 Block 1 +1.0000 1.0000

3.50 2-AminoBenzonitrile 99 Block 1 +1.0000 1.00003.51 Diethyl L-(+) tartrate 82 Block 4 4.1663.52 Peonile 89 Block 2 +5.0000 5.0000

Block 5 +6.0000 6.0000Block 6 +5.0000 5.0000

3.53 N,N-Dimethylbenzamide 96 Block 6 +1.0000 1.00004 REDUCTION 21.2871 11.5084 32.79554.1 Norcamphor 20 PP-3/4/5 0.0166 0.01664.2 4-Hydroxy Isoleucine 35 PP-8 3.3330 -3.2330 0.10004.3 Allofuranose Sugar 67 PP-3/4/5 0.0100 0.01004.4 Diethylamino Malonate Hcl 84 PP-8 +0.2500 0.25004.5 Acrylamide Purified 85 PP-3/4/5 +0.4000 0.40004.6 4-Hexyl Resorcinol 36 PP-3/4/5 0.4160 2.0000

Block -3 +1.58404.7 Anethol 76 PP-6 20.000 30.0000

Block -6 +10.00004.8 L-Methionine Sulfoxime 55 PP-7 0.0100 0.01004.9 3’-Amino-5’ Oh Thymidine

(Amino – T)14 R & D 0.0084 -0.0079 0.0005

4.10 2-(4-Morpholinyl)-8-Phenyl-[4h-1] -Benzopyran-4-One

7 Block -1 0.0084 0.0084

5 ALKYLATION 13.5913 3.0000 16.59135.1 NAP Sugar 61 PP-1 0.0500 +0.9500 1.00005.2 9,9-bis (methoxymethyl)

fluorene (FLU)98 PP-1 +1.0000 1.0000

5.3 MTSCNE 106 PP-1 +0.1000 0.10005.4 ONT-7-D & ONT-7-L 107 PP-1 +0.1000 0.10005.5 5'-ODMT-2’ OMe NiBu-

Guanosine O6 CE111 PP-1 +0.0840 0.0840

5.6 5'-ODMT-NiBu-deoxycytidine

113 PP-1 +0.0500 0.0500

5.7 5'ODMT-NiBu-dG (O6 CE) 118 PP-1 +0.0500 0.05005.8 N-Bz-DMTMOEC (N-

Benzoyl-(4,4’-dimethyoxytrityl) (methoxy ethyl)-cytidine

28 PP-2 0.0833 0.0833

5.9 5’ – ODMT, 2’ – O – Cpep,6N – Pivaloyl Adenosine

38 PP-2 0.0080 -0.0070 0.0010

5.10 5’ – ODMT, 2’ – O – Cpep,N2 – Ph – Ac – Guanosine

39 PP-2 0.0080 -0.0070 0.0010

5.11 5’ – ODMT, 2’ – O – Cpep, 4– N – Bz Cytidine

40 PP-2 0.0080 -0.0070 0.0010

7


- DecreaseFinal

5.12 5’ – ODMT, 2’ – O – Cpep,Uridine

41 PP-2 0.0080 -0.0070 0.0010

5.13 5'-Odmt-2'moe-T[5’-0 (4,4’-Dimethoxy Trityl) – 2’-0-(2-Methoxyethyl) – Thymidine]

44 PP-2 0.0580 +0.9420 1.0000

5.14 N – Bz – 5’ – Odmt – 2’ –Moe – 5 – Me – C 5’-0 (4,4’-Dimethoxy Trityl)–2’-0-(2-Methoxyethyl) N4 –Benzoyl–5-Methyl- Cytidine

45 PP-2 0.0300 +0.9700 1.0000

5.15 3-3 Dimethyl Cyclohexanone(DMCH)

25 PP-8 0.0833 +0.9167 1.0000

5.16 4-Methyl –2-ThiomethylPyrimidine

34 PP-3/4/5 0.417- -0.3770 0.0400

5.17 4,4'--DimethoxytritylChloride (DMT-CL)

56 PP-3/4/5 0.1500 +0.8500 1.0000

5.18 4-Tert-butyl phenoxy AceticAcid

92 PP-3/4/5 +1.0000 1.0000

5.19 GAFL-158 100 PP-3/4/5 +5.0000 5.00005.20 CMPT 104 PP-3/4/5 +0.0400 0.04005.21 CMIMT 105 PP-3/4/5 +0.0400 0.04005.22 7-Bromo 1heptene 53 PP-3/4/5 0.2200 4.0000

Block -3 +3.7806 ORGANOMETAL 0.0100 +2.5460 2.55606.1 2,2Bis[-(2indenyl) Bi

phenyl] Zicronium(Iv)Chloride

54 PP-7 0.0100 + 0.0400 0.0500

6.2 2,2Bis[-(2indenyl) Biphenyl]Zicronium(Iv) Chloride OnSilica Support

95 Block 3 +2.5000 2.5000

6.3 Ethylene diamine tetra acetic 86 Block 4 + 0.0030 0.0030Acid Metal Chelate Salts Block 5

6.4 Sodium Selenite Pentahydrate

87 Block 5 + 0.0030 0.0030

7 OXIDATION 0.4000 0.40007.1 Nootkatone 80 PP-2 0.4000 0.40008 R & D products 0.4000 0.40008.1 R&D Products (Intermidiates) 90 R & D lab 0.4000 0.4000

8

Sr.No.

Group ExistingCapacity

ProposedCapacity

TotalCapacity

MT / M MT / M MT / M1 Friedel-crafts products 75.0000 100.0000 175.00002 Acylation products - 89.2370 89.23703 Condensation products 7.7152 25.3320 33.04724 Reduction products 21.2871 11.5084 32.79555 Alkylation products 13.5913 3.0000 16.59136 Organometal products 0.0500 2.5060 2.55607 Oxidation products 0.4000 - 0.40008 R&D Products 0.4000 - 0.4000

Table no. 1.1 indicates that manufacturing of Friedal craft reaction productsconstitutes the major activity at site

1.6 Byproducts

The proposal involves increased byproducts recovery from 303.00 (MT/M) to

1200.00 (MT/M) as listed in the Table no. 1.2.

TABLE NO. 1.2: Byproducts

Sr. No. By-ProductExisting(MT/M)

Proposed(MT/M)

Total(MT/M)

1 Hydrochloric Acid 30% 43.00 464.50 507.50

2 Sulphuric Acid 66% 85.00 100.00 185.003 Mixed Solvents 133.50 426.5 560.004 Aqueous Aluminium Chloride 303.00 897.00 1200.00

1.7 Plants capacity

The Nature of the manufacturing activity is technology oriented . The

a) Manufacturing activity consists of following pattern & D activity

b) Kilo lab products

c) Pilot plant products

d) Large capacity plants

9

The company has identified NUCLEOSIDES & NUCLEOTIDES as its niche area

which arebasic building blocks of nucleic acids (DNA & RNA). Innovassynth

havealso earned reputation as a one of the leading manufacturer and suppliers of

various protected Nucleosides globally and working as a partner for Process research

with many pharma and drug discovery companies.

The Manufacturing activity involves undertaking job work concept hence work for

various parties is undertaken simultenously . This necessitates the need for number of

manufacturing locations for different scale of operations . In view of this there are

various dedicated manufacturing plants spread over various locations at site . Table

number 1.3 and Table number 1.4 gives Existing Plants capacity and proposed plant

capacities respectively.

TABLE NO. 1.3: Existing plants capacity

S.N Group Existing plants capacity in MT / MPP-1 PP-2 PP-3/4/5 PP-6 PP-7 PP-8 MPP R&D Lab

1 Friedel-crafts - - - - - 75 -2 Acylation - - - - - - -3 Condensation 1.1092 0.6110 2.9746 1.00 2.0100 - 0.01044 Reduction -

0.926620.00 0.010 0.3500 - 0.0005

5 Alkylation 2.3840 2.08738.1200

1.0000 - -

6 Organometal - - - - 0.050 - -7 Oxidation - 0.4000 - - - -8 R&D Products - - - - - - 0.4000

Total 3.4932 3.0983 12.0210 21.00 0.060 3.3600 75 0.4109

TABLE NO. 1.4: Expansion plants capacity

Expansion plants capacity in MT/ MS.N Group Block-1 Block2 Block3 Block4 Block5 Block6

1 Friedel-crafts 40.0000 20.0000 20.000 20.00002 Acylation 25.0000 28.000 39.23073 Condensation 1.0000 5.0000 1.1660 4.1660 6.0000 5.00004 Reduction 0.0084 1.5000 10.00005 Alkylation 3.00006 Organometal 2.5000 0.0030 0.00307 Oxidation8 R&D Products

Total 41.0084 50.0000 56.1660 4.1690 6.0030 74.2370

10

1.8 Groupwise number of products

The proposal involves activies such as scale up , scale down capacities , installaingnew manufacturing facilities. Table no. 1.5 indicates details of the changes for 119products .

TABLE NO. 1.5: Groupwise number of products

Number of productsNumber of Existing products New

Sr.no.

Group

No

capa

city

cha

nge

Elim

inat

ed

Cap

acit

y R

educ

tion

Cap

acit

y A

ddit

ion

Pro

duct

Tot

al

1 Friedal craft reaction products - - - 2 - 22 Acylation products - - - - 1 13 Condensation products 2 10 14 11 26 634 Reduction 4 6 2 1 3 165 Alkylation products 1 5 5 6 10 276 Organometal products - 3 - 1 3 77 Oxidation products - - - - 1 18 R & D Products - 1 - - 1 2

Total 7 25 21 21 45 119

Products (25 nos, ) are eliminated hence corresponding specific Raw materials forthose products will also be eliminated.The process , description , flow chart andmaterial balance for all the products are available in EIA report .

1.9 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 timeframe.

11

SECTION 2: HAZARD IDENTIFICATION

2.1 Preliminary hazard analysis ( project life concept )

Table no. 2.1: Layout Hazards

Layout Hazard

Pre

Con

stru

ctio

nph

ase

Con

stru

ctio

n ph

ase

Ope

rati

on p

hase

Pos

t O

pera

tion

/De

com

mis

sion

ing

/dem

olis

h

a) Increased fire/explosion hazard for the flammable solvent Tankfarm located below HT transmission line, unsafe condition forwater monitor movement during fire fighting operation .

√ √ √ √

b) Accidental release of hydrogen gas may travel towards the HTtransmission line tower located near hydrogenation plantLeading to fire /explosion hazard

√ √ √ √

c) Uncontrolled spread of accidental spill / washings at chemicaltanker parking area , may enter the water body

√ √ √

d) Access roads to site are passing below HT transmission line mayhamper emergency evacuation during earthquake , cycloneaffected power line .

√ √ √ √

e) Demolition and construction activity vehicles movement nearflameproof solvent storage / handling area spread over the site .

√

f) Ageing of plant issues such as under ground fire hydrant system, under ground cables at solvent handling also flameproofworthyness of electrical fittings

√ √ √ √

g) Organic contaminated water generated during fire fightingoperations , sprinkler operation , spill / floor washing may enterstorm drain .

√ √ √ √

In addition to above Annexure no. 7 lists additional detailed Hazards covering followingaspects for life time of the project considering following aspects

Natural calamities Physical hazards Biohazards Electrical hazard Hazardous substances and wastes

Mechanical hazards Frequent causes of accidents during construction Activity Ergonomics & psychosocial hazards General Hazards

12

2.2 FLAMMABILITY HAZARD

Table no. 2.2: Flammability hazards

Sr.No. Name LEL UEL FlashPoint

BoilingPoint

NFPA HazardIndex

MF

% % 0c 0c Nf Nr1 Hydrogen 4 76 Gas - 4 0 212 Diethyl ether 1.7 48 -45 35 4 1 213 Methyl chloride 8.1 17.4 - -24.2 4 0 214 Toluene 1.2 7 12.7 110.4 3 0 165 Ethanol 3.3 19 13 79 3 0 166 Isopropyl alcohol* 2 12.7 11.7 82 3 0 167 meta Xylene 1.1 7 27 139 3 0 168 Acetone 2.2 13 -17.7 56.48 3 0 169 Acetonitrile 4.4 16 5.6 82 3 0 1610 Ethyl acetate 2 11.5 -4 77 3 0 1611 Ethylene Dichloride 13 83.4 3 0 16

12 Hexane 1.2 7.7 -23 55 3 0 16NFPA 704 M Hazard Index, Scale 1 to 4.The Highest NFPA flammability Hazard ( Nf ) Rating is 4 for site chemicals

2.3 TOXICITY HAZARDTable no. 2.3: Toxicity Hazards

Sr.No.

Name NFPAHazardIndex

TLV STEL IDLH OralLD50

DermalLD50

Inhal.LC50

Nh Ppm Ppm Ppm mg/kg. mg/kg. mg/m3

1 PhosphorousOxychloride

3 0.1 380

2 Allyl Chloride 3 1 2 425 2066 58003 Allyl Bromide 3 120 50004 Sodium Hydroxide 3 2 mg5 Hydrochloric Acid 3 1 5 900 31246 Hydrogen Chloride 3 5 50 238 5010 31207 Phenol 3 5 317 6698 THF ( Tetrahydrofuran) 2 200 250 1650 210009 Methyl Chloride 2 50 1600 5200010 Toluene 2 100 500 636 14100 4900011 Isopropyl alcohol 2 200 400 5045 12800 1600012 m- Xylene 2 100 150 900 4300 >1700 5000

NFPA 704 M Hazard Index, Scale 1 to 4.The Highest NFPA Health Hazard Rating of 3 for site chemicalsSource: MSDS

13

2.4 Reactivity Hazard

Table no. 2.4: Reactivity HazardsSr.No.

Name NFPA Hazard Index Materialfactor

Nf Nr1 Phosphorous Oxychloride 0 2 242 Diethyl ether 4 1 213 THF(Tetrahydrofuran) 3 1 164 Diisopropyl Ether 3 1 165 Allyl chloride 3 1 166 Allyl bromide 3 1 167 Sodium hydroxide 0 1 148 Hydrochloric acid 0 1 149 Hydrogen chloride 0 1 1410 Hydrogen 4 0 2111 Methyl chloride 4 0 2112 Toluene 3 0 16

NFPA 704 M Hazard Index, Scale 1 to 4. ;The Highest NFPA Reactivity Hazard Rating of 2 is for site chemicalsMaterial factor scale 1 to 40The Highest Material factor of 24 is for Phosphorous Oxychloride

2.5 INVENTORY ANALYSIS

2.5.1 INVENTORY

There are 308 raw materials handled at the site . The list of location wise inventory detailsfor all materials storage is presented in the EIA report. The list is arranged in decendingorder of max quantity stored and contains chemicals with significant hazard .

Table no. 2.5: Hazardous Chemicals Inventory

Sr.No.

Name Consumption

Max.Qty.Stored(mt)

Mode of storage

1meta Xylene ( imported )

550.00 45.00 70 kl Tank , receipt by21 kl iso tanker

2 Aluminium Chloride 1500 41.00 400/250 kg Drum / Bag3 Sulfuric acid 98% 1100+800 39.00 Tank4 Cyanuric Chloride ( imported ) 672 36.80 Bags5 Methanol 2500.0 34.25 Tank6 Resorcinol ( imported ) 1000 27.40 Bags7 Heptane ( imported ) 213.80 17.00 Tank8 Hexane 2039.0 16.75 Tank

14

Sr.No. Name

Consumption Max. Qty.Stored

(mt)

Mode of storage

9 Methyl Iso Butyl Ketone (imported )

150 12.00 Tank

10 Dichloromethane 694.00 9.50 260 kg MS drums11 Propionyl Chloride 345.00 9.00 200 kg MS drums12 Ethyl acetate 3059.30 8.50 205 kg HDPE drums13 Benzotrichloride 1200.00 6.51 250 kg HDPE drums14 Allyl chloride 350.00 4.50 200 kg MS drums15 ODCB (ortho Di chloro

Benzene)100 4.00 250 kg GI drums

16 Toluene 115.0 3.50 174 kg MS drums17 Acetic Acid 418.20 2.25 35 kg HDPE carbouys18 Chloroform 359.00 1.95 290 kg HDPE drum19 Ammonia 140.35 1.90 35 kg HDPE carbouys20 Sodium Hydroxide 157. 75 1.60 50 kg drums21 Cyclohexanone 228.00 1.25 200 kg MS drums22 Potassium Hydroxide 87.00 1.19 50 kg bags23 Hydrochloric Acid 33% 210.00 1.15 40 kg HDPE carbouys24 Sodium hydride 215.8 1.15 125 kg MS drums25 Benzyl Cyanide 205.2 1.10 50 kg drums26 Acetonitrile 196.50 1.00 160 kg MS drums27 Ethanol 75.90 1.00 200 ltr HDPE drums28 Phosphorous oxychloride 73.60 1.00 50 kg HDPE carbouys29 Tetrahydrofuran 70.35 0.90 180 kg MS drums30 Bromine 60.40 0.83 3 kg Bottle31 Propionaldehyde 21.50 0.50 200 kg MS drums32 Dimethyl amine 36.00 0.49 35 kg HDPE carbouys33 Acetic anhydride 85.55 0.47 200 kg HDPE drums34 Dimethylsufide 34.20 0.47 200 kg MS drums35 Benzoyl Chloride 33.00 0.45 210 kg HDPE drums36 1,4-Diaxone 79.00 0.43 200 kg MS drums37 Benzene 83.56 0.40 200 kg MS drums38 Epichlorodrin 26.64 0.35 200 kg MS drums39 Thionyl Chloride 70.75 0.35 300 kg MS drums40 Acetone 54.40 0.30 200 ltr HDPE drums41 Sulphur 56.0 0.30 25 kg polyethylene bags42

Hydrogen87.14 0.09 45kg in a Quad of 20

cylinders43 Methyl Chloride Gas 13.82 0.08 Cylinder44 Hydrochloric gas 0.9 0.02 No storage45 Chlorine gas 0.14 .002 Cylinder

15

TABLE NO. 2.6: HAZARDOUS CHEMICALS CLASSIFICATION

Group

Material Max.StorageCapacity

ThresholdQty. Mt.*

2 Toxic chemicals Bromine 0.140 402 Toxic chemicals Chlorine 0.002 103 Highly reactive

chemicalsHydrogen 0.090 2

5.1 Flammable gases Methyl chloride 0.080 155.3 Very Highly Flammable

Liquids.Chemicals havingflash point ≤ 230 C &boiling point < 350 C

Less thanthreshold*

1500

5.5 Highly FlammableLiquids.

Chemicals having230 C < flash point ≤ 600C

Less thanthreshold*

2500

5.6 Flammable Liquids. Chemicals having600C < flash point < 900 C

Less thanthreshold*

5000

*Criteria used: “Manufacture Storage and Import of Hazardous Chemicals Rules, 1989”. The site is not a Major Accident Hazards (MAH) Installation.

2.6 RELATIVE RANKING

2.6.1 DOW F&E 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.

TABLE NO. 2.7: DOW F & E INDEX

Sr.No.

Installation DOW F&EIndex

The Degree OfHazard

Radius OfExposure (m)

DamageFactor

Toxicity Index ToxicityCategory

1 Hydrogen 59 Light 15 0.58 - -2 Methanol 34 Light 8.7 0.26 2.48 I3 Xylene 46 Light 10.5 0.39 3.46 I4 Furnace oil 17 Light 4.5 0.11 - -

2.6.2 MOND INDEX ASSESSMENT

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.

16

TABLE NO. 2.8: MOND INDEX ASSESSMENT

SR. NO. MATERIAL OVER ALL HAZARD RATING

1 Hydrogen 230 Moderate2 Methanol 940 High Group I3 Xylene 582 High Group I4 Furnace oil 255 Moderate

flammable solvents tank farm hazard index is highest amongst all the installations.

and need off setting measures. 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.

2.7 COMPATIBILITY/ REACTIVITY HAZARD

2.7.1 Hazardous RM Storage Area Location No 20

Table No. 2.9: Compatability /Reactivity Hazard Matrix

Chemicals Mixing With →

Am

mon

ium

Hyd

roxi

de

Ben

zyl C

hlor

ide

Bro

min

e

Form

alde

hyde

Hyd

roch

lori

c A

cid

N-B

utyl

Alc

ohol

Thi

onyl

Chl

orid

e

Ammonium HydroxideBenzyl Chloride CBromine N NFormaldehyde C C NHydrochloric Acid N C N NN-Butyl Alcohol Y Y N C CThionyl Chloride N Y N N N N

CHART LEGEND

Y Compatible - No hazardous reactivity issues expectedN Incompatible - Hazardous reactivity issues expectedC Caution - May be hazardous under certain conditionsSR Self reactive - Potentially self reactive e.g. polymerizable

17

2.7.2 TRANSFORMATION PRODUCTSHazards due to gases released decpmposition , transformation during fire condition .

Table No. 2.10:Transformation If Any Which Could Occur

SR.NO. NAME DECOMPOSITION PRODUCTS IN CASE OF FIRE1 Aluminium

chlorideRelease of Hydrogen chloride gas when incontact with water

2 Benzyl cyanide Release of Toxic gases in contact with acidsleading to cyanide poisoning

3 Benzyl chloride Hazardous polymerization can occur in presence ofcatalytic impurities such as aluminum, iron, rust, orsodium acetate + pyridine + iron at 115C

4 Thionyl chloride Decomposes to Hydrogen chloride and sulfur trioxide when in contact with water

a) Store chemicals considering the compatibility and reactivity hazards at tankfarms, stores and warehouses.

b) A cyanide antidote kit should be kept in immediate work area and must beavailable rapidly available .

2.7.3 LABORATORY CHEMICALS

There is large number of laboratory chemicals , The inventory and location s aredetailed in annexure 2 . Any accidental mix up of the chemicals may lead to unsafecondition , smouldering , fire , explosion depending upon the chemicals involved

18

2.8 HAZOP STUDY

2.8.1 Identification of hazards by HAZOP study is carried out for following nodes ,

the thrust area being the environmental issues in the proposed activities. The

HAZOP Study carried out under batch wise modes following NODES

Table No. 2.11: Nodes For Hazop Study

Sr.no. NodeNode 1 Tank Farm.Node 2 Friedal craft reaction productsNode 3 Acylation productsNode 4 Condensation productsNode 5 Reduction productsNode 6 Alkylation productsNode 7 Organometal productsNode 8 Oxidation productsNode 9 R & D ProductsNode 10 Solvent Recovery.Node 11 ETP.

2.8.2 The methodology used as per Hazard Identification and Hazard Analysis

Techniques of Hazard Identification And Risk Analysis – Code Of Practice Is

15656: 2006.

2.8.3 Hazard are identified and risk evaluated for each identified hazard on the

scale 1 to 25 using the hazard rating matrix given in table 2.12

Table No. 2.12:

HAZARD RATING MATRIX.

SEVERITY

PR

OB

AB

ILIT

Y

VeryHigh(5)

High.(4)

Moderate(3)

Slight(2)

Nil.(1)

Very Likely. (5) 25 20 15 10 05Likely. (4) 20 16 12 08 04Quite Possible (3) 15 12 09 06 03Possible. (2) 10 08 06 04 02Not Likely. (1) 05 04 03 02 01

2.8.4 Process description , material balance and flow charts for all the products

including the eliminated products are available in the EIA report .Typical

products having bulk manufacturing , using hazardous chemicals and

processes are reproduced here to avoid repitation of data . Only

19

Product no 75 p- Anisyl Propanal

Manufacturing Process:Step 1:p-Anisic aldehyde under goes condensation reaction with propionaldehyde in presenceof Sodium hydroxide which will give an Intermediate Product.After distillation of Intermediate Product recovered Product under goes hydrogenationreaction in presence of catalyst, Hydrogen & Methanol which will give a Crude FinalProductAfter distillation of above Crude Product we will get Final Pure Product.Chemical Reaction:

OCH3

HO

+ CH3 H

OCH3

H O

OCH3

MeOH ; NaOH

Sulfuric Acid ; Toluene

Mol Formula: C8H8O2Formula Wt: 136.147

Mol Formula: C3H6OFormula Wt: 58.079

Mol Formula: C11H14O2Formula Wt: 178.227

FLOW CHART:

p-Anisic Aldehyde 0.984 kg)Methanol (0.255 kg) REACTORPropionaldehyde (0.451 kg)Sodium Hydroxide (0.0136 kg)Sulfuric Acid (0.023 kg) Methanol(0.8364) Toluene (0.063 kg) WORKUP Toluene (0.059 R)Sodium bicarbonate (0.0194 kg) To ETP (1.0292kg)Water 1 kg

20

DISTILLATION By productResidue (0.014 kg)INTERMEDIATE PRODUCTSodium Bicarbonate (0.020 kg)Methanol (3.0 kg) HYDROGENATION Catalyst (0.0026kg)Hydrogen (0.015 kg)

DISTILLATION Methanol (2.9kg) Vapour loss (0.4774 kg)1 kg PRODUCT Residue (0.098 kg)

NO Total Input: 5.8466 Kg Total Output: 5.7836 Kg Unit

1 Effluent generation per batch 1.0292 Kg2 Batch out put 1 Kg3 Effluent generation per kg 1.0292 Kg

1 Water consumption per batch 1 Kg2 Batch out put 1 Kg3 Water consumption per kg 1 Kg

Product no 76 AnetholeManufacturing Process:Step 1:Anisole is converted in 4-methoxypropiophenone by Friedel crafts acylation withpropionyl chloride.Step 2:The 4-methoxypropiophenone (ketone) is hydrogenated to the corresponding 1-(4-methoxyphenyl) propan-1-ol (alcohol) with appropriate catalyst.Step 3:The 1-(4-methoxyphenyl) propan-1-ol (alcohol) is dehydrated in presence of acidiccatalyst to give Anethole

21

FLOW CHART:

Anisole (0.99 kg)Sodium Chloride ( 0.15kg)AlCl3 (1.3 kg) REACTORPropionyl Chloride (0.96 kg) Dil. Aq. AlCl3(5.49569kg) Sodium bicarbonate(0.057kg)Water (3.25 kg)Methanol (0.134 kg)Raney Nickel (0.007 kg) Methanol(0.0938 kg) Hydrogen (0.0310 kg) REACTION MASSRaney Ni (0.01 kg) Triethyl amine (0.0029 kg)TEA (0.00203 kg)Divyol-460 oil (0.0006 kg)Potassium Hydrogen REACTION MASSsulphate (0.0029 kg) EDC (0.105 kg)EDC (0.15 kg) Vapour loss (0.08607kg)

Product Anethole (1 kg)

By Product Dihydro Anethole0.06kg

Anethole Polymer0.17kg

NO Total Input: 7.02259Kg Total Output: 7.02259Kg Unit

1 Effluent generation per batch 5.49569 Kg2 Batch out put 1 Kg4 Hazardous waste 0.33 KG

1 Water consumption per batch 3.25 Kg2 Batch out put 1 Kg

22

NODE 1 OF 9 : Tank Farms and ware housesDESIGN INTENT : Receipt , storage and transfer to plant operations

Guide Word Parameter Deviation Cause Consequence ProtectionMeasures

S P R ActionSuggested

None. Inventory NoInventory

Products 25 nos are eliminated hencecorresponding specific Raw materials forthose products will also be eliminated

Unsafecondition

SOP.

Supervision.

3 3 9

There are number of tank farms and warehouses spread over the site as indicated in the following table . Details of the each storage facility aregiven in the EIA report .

Location Block no. Description No. of chemicals Remark7 BTL RM store room 185 Non-Flammable

17 PP-6 RM store 2 Non-Flammable solids17 PP-6 RM store 5 Non-Flammable , Toxic19 Solvent tank farm 3 Flammable solvents20 Hazardous RM storage area 3 Corrosive20 Hazardous RM storage area 14 Non-Flammable , Toxic21 Solvent tank farm 13 liquids Flammable , non Flammable , Toxic21 Solvent RM store room 2 Non-Flammable solids21 Solvent RM store room 61 Non-Flammable , Toxic26 Hydrogenation plant & hydrogen gas cylinder store area 1 Hydrogen32 BASF RM STORE 7 Non-Flammable35 Solvent Tank farm 2 Flammable40 Corrosive material storage tanks 3 Acid , alkali43 Tank farm 1 Benzene44 Toxic RM storage room 1 Benzyl Cyanide45 Hazardous Gas Cylinder store area 4 Gases47 Tank farm 1 MIBK

23

NODE 1 OF 9 : Tank Farms and ware housesDESIGN INTENT : Receipt , storage and transfer to plant operationsGuideWord Parameter Deviation Cause Consequence

ProtectionMeasures S P R Action Suggested

AsWellAs.

Effluent Effluentgeneration.

Fire fighting operation ,sprinkler water , spill ,floorWashings will generateorganic contaminatedwater

Environmentalissues.

ETP provided. 3 3 9

Other. Flow. Static charge. Static sensitive materialhandling and sampling ,dispensing operations offlammable solvents

Static charge assource ofignition, firehazard.

Equipments areearthed

3 3 9

OtherThan.

Flow Un intendedmix up

Accidental mix up , spill, floor washings mix upin drain systemWrong valve operation attank farm ,Dyke partitionfailure etc.

Reactivity andcompatibilityhazardsdepending uponthe compoundsinvolved .

DedicatedpipingSupervision

4 4 16 Separate chemicalsstorage in bulkconsidering thecompatibility andreactivity hazards attank farms, storesand warehouses.

More. Temperature. Moretemperature.

Summer season Emission at vent.Pressurization ofcontainers of lowboiling solventse.g MDC

Temperaturecontrol at warehousesSupervision.

3 3 9

Less. Temperature. Lesstemperature

Winter season Freezing ofmaterial e.g.Acetic acidGlacial ( meltingpoint 16.7 0c )

Supervision 3 3 9

24



More. Pressure. More Pressurewhiletransferring.

Valve failure or closed inerror.

Gasket failure.

Spill hazard. PI. 3 3 9 Provide splashguards over flangejoints carryingcorrosive materialsacid / alkali underpressure to preventsplashing of acidleaking throughjoints due to gasketfailures

Less. Pressure. Less Pressure. Tank Vent blockagewhile pumping out.

Implosion.

Spill hazard.

Supervision. 3 3 9 Regular inspection ofvent.

OtherThan.

Composition. Unintendedcomposition

Decomposition productse.g water reactivechemicalsFire conditionsSide reaction products

environmentalissues.

Quality andprocess controlchecks

3 3 9 Obtain MSDS ofimpurities (if any), inabsence of theinformation thechemicals should betreated as ifhazardous chemicals.

More. Level. Higher level atday tank atplant

Overfilling due tooperator error.

Spill hazard. 1. LI.2. Supervision.

3 3 9 Consider overflowline back to the tankof origin.

25



Less. Level. Less level attanks orinventory

Decommissioning of the25 nos Products Leftover / residual specificRaw materials for thoseproducts

Unsafe condition SOP.

Supervision.

4 4 16 .Ensure safe disposalof Unused or the leftover specific rawMaterials of the

eliminated products

Other Location Location closeto source ofignition

Flammable solvent Tankfarm from Block locationno 19 near HTtransmission line

Unsafe condition Flameproof area 4 4 16 Relocate Flammablesolvent Tank farmfrom Block locationno 19 near HTtransmission line toBlock location no.35.

Other. Hazardouswaste.

Solid wastegeneration.

Empty containers willcontain hazardous waste/residual materials

Disposal of usedcontainers /drumsEnvironmentalissues.

Hazardous solidwaste disposalto CHWTSDF.

4 4 16

Other. Handling. Parking of theroad tankers

organic contaminatedwater generated duringfire fighting operations,sprinkler operation,accidental spill / floorwashing at parkinglocations percolating /entering water body

Pollution issuesof the water body

Fire protectionsystem atparking lots

4 4 16 Provide FWCP (firewater catchment pit)forcollection of suchstreams andsubsequenttreatment procedurebefore disposal.

26



Other. Handling. solventshandling

Hstorage and handling ofSolvents such as MetaXylene ,MethanolHeptane ,HexaneMIBK , MDC ,EthylAcetate, ODCB ,Benzene ,Toluene,ChloroformAcetonitrile ,EthanolTetrahydrofuran ,Dimethyl Amine1,4-Diaxone ,Acetone

Fire /explosionhazardHealth hazard

Flameproofelectrical ,spark arrestorsat vehiclesexhaust

Storage insecure andbounded area.

Dyke foraccidental spillcontainment forabove groundstorage tanks

Portable fireextinguishers.Fire Hydrantsystem.

Display ofMSDS

4 4 16 Provision of PPE,SCBA.Warning signs.

Flame arrestor attank vent.

Smoke detector ,

HC leak detector

Static charge controlmeasures ( earthing )Emergencyprocedures.

Ventilation.

Spill cleanupmaterials.

27



Other. Handling. Toxicdecompositionproducts

Toxic RM storage roomBlockage location no 44, storage of Benzylcyanide , release ofToxic gases on contactwith acids .

Health hazardCyanosis

Isolated storageSecured ,restricted entrystorage

4 4 16 SOP for handlingbenzyl cyanide

Other. Transportationof hazardousmaterials

Flammable ,toxic materialstransport onroad outsideand at site

Flammable solventsToxic materials

Fire /explosionHealth hazard onexposure

Spark arrestor.Display of classlabels. Validregistration tocarry the saidgoods.PPE, First aidbox, tool box,safetyquipments,TREM card.MSDS

4 4 16 Training to drivers.Specifiedpredeterminedroutes.Atidotes as may benecessary to containan accident.

Other Emergency Spill / releaseof flammablegas

Accidental spill of metaxylene / release offlammable gas –Hydrogen / toxic gas-Hydrogen chloride gasat storage

Pool fire in dykeTank fireVapor cloudexplosion

Fire hydrantsystem

4 4 16 Estimate the ofconsequence of suchaccident sceneriosmeta xylene poolfire VCE ofHydrogen gasrelease ;Hydrogenchloride gas releaseand dispersionfollowed by DMP

28

NODE 2 OF 9 : Friedal craft reaction productsDESIGN INTENT :

GuideWord

Parameter Deviation Cause ConsequenceProtectionMeasures

S P R Action Suggested

More Manufacturingcapacity

Increase inmanufacturingcapacity

Expansion in existingMPP and addition of newplants of 20 mt/m capacityfour plants at block no 1,23 and 6 .

The material handlingspread ovr the site .

Supervision 3 3 9

More. ProcessEmissions.

More Vent gases. VOC.Residual reactantsHydrogen chloride gas isone of the reactant

Environmental issues. Scrubber at eachplantInterlock withagitationHydrochloric acidas byproduct

5 4 20 Leak detector at thevent of scrubber

More. FugitiveEmissions

More concentrationof chemicals inwork place air

Reactor Pump gland leak

Receivers vents

Minor spills

open handling ofchemicals

Health hazard Dedicated closedpipwork forchemicals transfer

Equipment ventingthrough scrubbersystem.Preventivemaintenance forpumps.

5 4 20 Monitoring of airborn concentration ofchemicals in workplace.

Periodic medicalsurveillance of theemployees.

Reverse Flow. Reverse flow of airin system

Power failure duringrecovery of solvent bydistillation.

Ingress of air to hotflammable solvent inthe distillation system.

Fire/ explosion hazard.

SOP.

Supervision.

3 3 9 Provide Nitrogen forbreaking vacuumduring solventrecovery bydistillation.

As Well As. Effluent Effluent generation. Hydrolysis products ofAluminium chloride

Environmental issues. ETP provided. 3 3 9

Other. Flow. Static charge. Static sensitive materialhandling.

Static charge as sourceof ignition, fire hazard.


3 3 9

29


GuideWord



Other Than. Flow unintended mix up Accidental mix up , spill ,floor washings mix up indrain systemWrong valve operation

Reactivity andcompatibility hazardsdepending upon thecompounds involved .

Dedicated pipingSupervision

4 4 16

More. Temperature. More temperature. Reaction exotherm

Product no 17 , substitutedTriazine derivatives , FCreaction using Resorcinolvigorous , development ofHydrogen chloride gas isexpected .

Emission at vent. TICSupervision.Scrubber

3 3 9

Less. Temperature. Less temperature Excessive cooling. Not significant. – – –More. Pressure. More pressure. Reaction exotherm. Not significant System vented

through scrubber3 2 6 Provide SRV on the

jacket of the reactorshandling low boilingsolvents.

Less. Pressure. Less pressure atreactor.

Vacuum in the system.

Fast pumping out and ventclosed.

Fast cooling, vent closed.

Not significant. Equipments aredesigned forvacuum.

– – –

More.Phase. More phases. Agitation loss (loss of

power, mechanicalproblem etc.).

Disturbed operation SOP.

Supervision.

3 3 9

As Well As. Composition Impurities . Impurities. environmental issues. Quality andprocess controlchecks

3 3 9

30


GuideWord



Other Than. Composition. Unintendedcomposition

Decomposition productsFire conditionsSide reaction products




More. Level. More level. Human error.Excessive charging of batch

Entrainment,ingress ofmaterial in ventline.

Sight glass/ glassequipment.

3 1 3 Provide vacuum trapin vacuum line.

Less. Level. Less level. Less batch charging.Human error.

Thermowell maynot dip.Unsafe condition.

SOP.

Supervision.

2 2 4

Other. Hazardous waste. Solid wastegeneration.

Spent catalyst.

Residue.


Hazardous solidwaste disposal toCHWTSDF.

3 3 9



Flameproofelectrical ,Portable fireextinguishers.Fire Hydrantsystem.Display of MSDS

4 4 16

Other Handling. Water reactivechemicalsAluminiumchloride

reacts violently with water ormoisture releasing toxic andcorrosive hydrogen chloride fumesand heat. Old containers may explodeon opening.

Pressurization ofcontainers Healthhazard

Supervision 4 4 16 SOP for waterreactive chemicalsstorage and firefighting

Other Handling. Water reactivechemicalsCyanuricchloride

The substance decomposes onheating producing toxic andcorrosive gases. Reacts violentlywith water producing cyanuric acid,hydrochloric acid and heat

Pressurization ofcontainers Healthhazard

4 4 16 SOP for waterreactive chemicalsstorage and firefighting

31

NODE 3 OF 9 : Acylation productsDESIGN INTENT : 2, 4 di hydroxyl benzophenone manufacture

GuideWord Parameter Deviation Cause Consequence


None. Manufacturingcapacity

New product atsite

New facility for89.2370 t / mcapacityptroposed atBlock 2 , 3 and6 .

It is newproductmanufacture inbulk at site

R& D , kilo laband PP systembeforedeveloping newproducts .

3 3 9 Provide scrubber forHydrogen chloride atblock no. 2,3 and6.Production plants are

More. Process Emissions. More Vent gases.Release ofhydrogen chloridegas in process

VOC.Residual reactantsReleased gases inprocess


Scrubber toproduce 30 %hydrochloric acidas byproduct . .

5 4 20 Provide leak detector atvent of the scrubber .Interlock it with reactorstirring .

More. Fugitive Emissions Moreconcentration ofchemicals in workplace air

Reactor Pumpgland leak

Receivers vents

Minor spills

open handlingof chemicals



5 4 20 Monitoring of air bornconcentration of chemicals inwork place.

Periodic medical surveillanceof the employees.

Reverse Flow. Not anticipatedAs WellAs.


Mother liquor atcrystallizationstep &Washings.


ETP provided. 3 3 9

32




Other. Flow. Static charge. Static sensitivematerialhandling.



3 3 9

OtherThan.

Flow unintendedmix up

Accidental mixup , spill , floorwashings mixup in drainsystemWrong valveoperation



4 4 16


Excessiveheating.

Emission atvent.

TI.Supervision.

3 3 9 Provide temperaturecontroller for steam lineat hot water system.


Excessivecooling.

Not significant - - -

More. Pressure. More pressure. Reactionexotherm.Excessive

heating whenlow boilingmethanolsolvent insidereactor.

Not significant System ventedthroughscrubber

3 2 6 Provide SRV on thejacket of the reactorshandling low boilingsolvents.

33





Vacuum in thesystem.

Fast pumping outand vent closed.

Fast cooling, ventclosed.


– – –

More. Phase. More phases. Agitation loss (lossof power,mechanicalproblem etc.).

Disturbedoperation

SOP.

Supervision.

3 3 9

As WellAs.

Composition Impurities . Impurities. environmentalissues.


3 3 9

OtherThan.


DecompositionproductsFire conditionsSide reactionproducts



3 3 9 Obtain MSDS of impurities (ifany), in absence of theinformation the chemicalsshould be treated as ifhazardous chemicals.

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


Sight glass/glassequipment.

3 1 3 Provide vacuum trap invacuum line.

34




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

Thermowellmay not dip.Unsafecondition.

SOP.

Supervision.

2 2 4



Not applicable

Handling. Corrosion. Acid handling Acidic streams arecorrosive.

Corrosion. MOC of anyequipment incontact with acidgases and waterconstructed in acid-resistant materialsor internallycoated.

3 3 9


Methanolhandling


Flameproofelectricals,


Provision ofPPE, SCBA.Warning signs.

4 4 16

Flame arrestor at tankvent.

Static charge controlmeasures ( earthing )Emergency procedures.

Ventilation.

Spill cleanup materials.

35

NODE 4 OF 9 : Condensation productsDESIGN INTENT : Condensation products as listed in Table 1.1

GuideWord

Parameter Deviation Cause Consequence ProtectionMeasures



More Vent gases.Distillationoperations may bea source ofemissions.


Emissions at vent.


Reflux condenser.

Reactor emissionsare generally small.

3 3 9


Moreconcentration ofchemicals in workplace air


Receivers vents

Minor spills




5 4 20 Monitoring of air bornconcentration ofchemicals in work place.

Periodic medicalsurveillance of theemployees.

Note :Condensation is the chemical reaction in which two or more molecules combine and expel water, an alcohol or another low-molecular

weight compound. Each of the reactants contributes a part of the separated compound. There is some overlap with addition reactions since the

initial step in condensation is addition.Specific waste water volumes are generally low, effluents mainly consist of reaction water if recycling

after phase separation is not possible. The effluent is composed of high-boiling components (condensation products/by-products) that often show

moderate or poor biodegradability, and low-boiling components (educts) with better biodegradability.

36




Reverse Flow. Reverse flowof air in system

Power failureduringrecovery ofsolvent 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. Generation ofeffluent.

Waste waterstreams fromprocess.

The effluent iscomposed ofhigh-boilingcomponents(condensationproducts / by -products) thatoften showmoderate or poorbiodegradability,and low - boilingcomponents(educts) withbetterbiodegradability.

Specific wastewater volumesare generallylow, effluentsmainly consistof reactionwater ifrecycling afterphaseseparation is notpossible.

ETP provided.

3 3 9

37







3 3 9

OtherThan.

Flow ununtendedmix up

Accidental mixup , spill , floorwashings mixup in drainsystemWrong valveoperationDyke failureetc.



4 4 16


ModerateReactionexotherm

Emission atvent.

TI.Supervision.


38




More. Pressure. More pressure. ModerateReactionexotherm

Faster additionof controlledreactant.Excessiveheating whenlow boilingsolvent insidereactor.


3 2 6 Provide SRV on thejacket of the reactorshandling low boilingsolvents.

Less. Pressure. Less pressureat reactor.


Fast pumpingout and ventclosed.

Fast cooling,vent closed.


– – –

39




Less. Temperature.

Lesstemperature

Excessivecooling.

Not significant. – – –

More.

Phase. More phases. Agitation loss(loss of power,mechanicalproblem etc.).

Disturbedoperation

SOP.

Supervision.

3 3 9

As WellAs.



3 3 9

40




OtherThan.





3 3 9 Obtain MSDS ofimpurities (if any), inabsence of theinformation thechemicals should betreated as if hazardouschemicals.

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


Sight glass/glassequipment.




SOP.

Supervision.

2 2 4



Residue. Environmentalissues.

Hazardous solidwaste disposalto CHWTSDF.

3 3 9

41






Flameproofelectrical ,spark arrestorsat vehiclesexhaustStorage insecure andbounded area.Dyke foraccidental spillcontainment forabove groundstorage tanksPortable fireextinguishers.Fire Hydrantsystem.Display ofMSDS

4 4 16

Provision of PPE, SCBA.Warning signs.

Flame arrestor at tankvent.

Smoke detector ,

HC leak detector

Static charge controlmeasures ( earthing )Emergency procedures.

Ventilation.


42

NODE 5 OF 9 : Reduction productsDESIGN INTENT : Products having Reduction step using hydrogen , product nos. 14 step 3 , 75 step 2 , 76 step 2 , 84 step 2




Increase incapacity

Product no. 76Anethol capacityincreased from 20Mt/m to 30 Mt/M byadding newmanufacturing facilityat Block 6

Hydrogen storage andhydrogenation process iscarried out at location blockno. 6 , the proposedexpansion is across the roadmay require hydrogenhandling crossing the road .Unsafe

Existing dedicatedhydrogen storage andhandling facility atlocation no. 26.

4 4 16 Hydrogen storage andprocess should bedeveloped at onelocation only .Avoid hydrogenhandling at number oflocations .Reduce the hydrogeninventory to 0.09 Mt.Optimize andmaintainthe inventory level ofallhazardous chemicals.

None. Flow. No flow. No material in thecylinders.

Isolation valve failure,closed in error.PRV malfunctioning.

Delayed operation. PI provided.

Preventive maintenance.

2 2 4 MSDS displayAuthorizedpreprocessors forrecovery /disposal ofhydrogenationcatalyst

More. Flow. More flow. More flow ofHydrogen.

Release of unreactedHydrogen at vent/pressurization.

Vent. 5 3 15 Provide flamearrestor in vent ofHydrogen vents andlocate flame arrestorsat to convenient placefor ease ofmaintenance.

43




Less. Flow. Less flow. Leak transfer lineblockage/ leak.

Release of Hydrogen. Fireand explosion hazard atHydrogen cylinder storageinstallation.

SOP. 4 4 16 Hydrogen leakdetector.

As Well As. Flow. Effluentgeneration inprocessoperation.

Waste water streamsfrom process.

Environmental issues. ETP provided. 3 3 9

Reverse. Flow. Reverse flow. Reverse flow atHydrogen feed line.

Dip pipe in the reactor, feedline fracture, siphon.

NRV in Hydrogen feedline.

4 3 12

Other. Flow. Static charge. Handling of staticsensitive materialssuch as Hydrogen.

Fire / explosion hazard. Flameproof electricalconfirming to Class IICfor Hydrogen.

3 3 9 Provide effectivemeasures forprevention ofaccumulation of staticcharge to a dangerousextent.

Other. Flow. Loss ofcontainment.

Catastrophic failure ofcylinder involved inlocal fire.

Fire/ explosion. Fire hydrant system.Prohibition of IgnitionsourcesFlame arrestor at ventPiping color codeFEA.safety training tooperativesSpark arrestor at vehicleexhaust

5 4 20 Shed for hydrogentrolleyFire hydrant systemHydrogen gas leakdetectors with alarmWater SprinklerAvoid uncontrolledgrowth of vegetationnear shed.EmergencyinstructionsDMP and Mock drill.

44





More rate of additionof Hydrogen.

Temperature rise asHydrogenation is anexothermic reaction.

Hydrogenation is anmild exothermicreaction and theequilibrium usually liesfar towards theHydrogenated productunder most operatingtemperatures.

3 3 9

More. Pressure. More pressure atreactor.

Reaction exotherm.PRV failure, morefeed in error,accidental mix up,utility failureLoss of cooling toreactor

Pressurization.

Explosion hazard..

Interlocks for highpressure , hightemperature at reactorPressure reliefarrangement

4 4 16 All pressure safetyvalves should be setat 10 % higher thanthe maximumachievable workingpressure.Prepare “DMP / OnSite Emergency Plan”based on MCLSStudy.Provide fire hydrantsystem.


Vacuum in the system.

Fast pumping out andvent closed.


Not significant. Equipments aredesigned for vacuum.

– – –

45




Other Than. Composition. Other thandesired material.

Oxygen in Nitrogencylinder in error.

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


Vent gases. VOC.Hydrogen unreacted.

EmissionsEnvironmental issues.

Flame arrestor.

Leak detector.

3 3 9

As Well As. Effluentgeneration.

Spill Washings. Environmental issues. ETP provided. 3 3 9

More.

Phase. More phases./phase separationGas – liquidphase process.

Agitation loss (loss ofpower, mechanicalproblem etc.).

Disturbed operation SOP.

Supervision.

3 3 9


DecompositionproductsFire conditionsSide reaction products

environmental issues. Hydrogenation reactionsgenerate little or nounwanted by-products.Quality and processcontrol checks


More. Level. More level. Human error.Excessive charging ofbatch

Entrainment, ingress ofmaterial in vent line.


3 1 3 Provide vacuum trapin vacuum line.

Less. Level. Less level. Less batch charging.Human error.

Thermowell may not dip.Unsafe condition.

SOP.

Supervision.

2 2 4

46



ProtectionMeasures S P R

ActionSuggested


Fire /explosion hazardHealth hazard

Flameproof electrical ,Fire protection system

4 4 16

Other. Handling. Hydrogenationcatalyst.

Raney nickelHydrogenationcatalyst preparation insolvent

Fire hazard Aqueous medium usedto reduce the fire hazardin handling of thehydrogenation catalystNitrogen inertingSupervision

4 3 12 SOP forhydrogenationcatalyst handling

Other. Handling. SpentHydrogenationcatalyst.

Spent Hydrogenationcatalyst.-Solid wastedisposal

Environmental issues. The spent catalysts aresent to authorizedrecyclers

3 3 9

Other. Handling. Hydrogencylinder abuse instorage &handling.

Hydrogen cylinderhandling.

Leak valve failure/piping failure.

Local fire.

Hydroegn release.

Fire/ explosion hazard.

Flame proof electrical. 5 4 20 Provide shed forstorage of Hydrogencylinder, watersprinkler Firehydrant system.

Training toemployees.

Provide Hydrogenleak detector.

Other. Handling. Emergency. Hydrogen iscombustible in air andOxygen over widerconcentration limitsthan most other gases.

Flammable mixtures in aconfined space will explodeif ignited by a flame orspark.Fire/explosion.

4 3 12

NODE 5 OF 9 : Reduction products

47

DESIGN INTENT : Other ProductsGuideWord


S P R ActionSuggested

Less Solventrecovery

Poor solventrecovery

Product no 55 ,methanol recovery is90 %

Environmental issues Supervision 4 4 16 Consider secondarycondenser

More Emission Poor solventrecovery

Product no 55 ,Chloroform recoveryis 90 %

Environmental issuesHealth hazard

Supervision 4 4 16 Consider secondarycondenserConsider adsorptionfor chlorioformreduction in vent

As well as Solid waste Residual Zinc Product no 86,Chloroform recoveryis 90 %

Disposal issue sent to authorizedrecyclers

4 4 16

Other Handling Sodium borohydrate

Product no 67 Sodiumboro hydrate used , itis water reactivematerial

Supports combustion.Flammable solid. Can ignitein air from an open flame,continuing to burn ashydrogen is evolved. Itreacts with water or steamto produce flammablehydrogen.

Supervision 4 4 16 SOP

Other Unitoperations

PurificationDistillation

Product no 85 is onlydrying and product no.35 is vacuumdistillation

Not significant Supervision - - - Reclassify theproducts

Other than Emission Released gasesin process

Carbon di sulfide usedin Product no 7 andHydrogen sulfide isreleased

Helath hazard Scrubber 4 4 16 Provide leakdetector at the ventof Hydrogen sulfidescrubber

48

NODE 6 OF 9 : Alkylation productsDESIGN INTENT : Alkylation products as listed in table 1.1



None. Manufacturing capacity

New product atsite

New facility forfor 7 Bromo 1heptane atblock 3 Productno 53

It is newproductmanufacture inbulk at site

R& D , kilo laband PP systembeforedeveloping newproducts .

3 3 9

Alkylation is the introduction of an alkyl group into an organic compound by substitution or addition. There are six types of alkylation reaction;

Substitution for Hydrogen bound to Carbon. Substitution for Hydrogen attached to Nitrogen. Substitution for Hydrogen in a Hydroxyl group of an Alcohol or Phenol. Addition to a metal to form a Carbon-metal bond. Addition to a Tertiary Amine to form a quaternary Ammonium compound. Miscellaneous additions to Sulphur or Silicon.

Alkylation is commonly carried out in liquid phase at temperatures higher than 200 ºC at above atmospheric pressures. Sometimes vapour phase

alkylation is more effective. Alkylation agents are usually olefins, alcohols, alkyl sulphates or alkyl halides. Catalysts are HF, sulphuric acid or

phosphoric acid. Lewis acids, like aluminum trichloride or boron trifluoride, may also be used as catalysts.

Chemical reaction

49





More Vent gases.

Release ofhydrogen chloridegas in process



VOC emissionsfrom alkylationreactions tendto be lowcompared withother unitprocesses.

5 4 20




Receivers vents

Minor spills






Reverse Flow. Not anticipatedAs WellAs.


Waste processstreamsWashings.


ETP provided. 3 3 9




3 3 9

50




OtherThan.

Flow unintendedmix up




4 4 16


Excessiveheating.

Emission atvent.

TI.Supervision.



Excessivecooling.

Not significant - - -

More. Pressure. More pressure. Reactionexotherm

Pressurization.

Explosionhazard.

SOP.

Moderateexotherm foralkylationreactions

4 3 12

Provide adequatepressure relief system(RD and dump tank) forthe reactor carryingexothermic reactions toavoid uncontrolledrelease of chemicals incase of accidentalpressurization.All pressure safety valvesshould be set at 10 %

51




higher than the maximumachievable workingpressure.Prepare “DMP/ On SiteEmergency Plan” basedon MCLS Study.Provide fire hydrantsystem.



Fast pumping out /cooling and ventclosed.


– – –


Disturbedoperation

SOP.

Supervision.

3 3 9

As Well As. Composition Impurities . Side reactionproducts.

Generally the useof lower alkylhalides leads to theformation of avariety of lowermolecularcompounds.

SOP.

Supervision.Process control test

3 3 9

52




OtherThan.





3 3 9 Obtain MSDS of impurities(if any), in absence of theinformation the chemicalsshould be treated as ifhazardous chemicals.

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

Entrainment,ingress of materialin vent line.





SOP.

Supervision.

2 2 4



Not applicable

Handling. Corrosion. Acid handling Acidic streams arecorrosive.


3 3 9


Flammablesolventshandling


Flameproofelectricals,

FEA

4 4 16

53

NODE 7 OF 9 : Organometal productsDESIGN INTENT : Organometal products as listed in Table 1.1




Increase inmanufacturingcapacity

From Pilot plantoperations increasein capacity to bulkmanufacturing .Product no 95capacity is highestto2.5 mt/m

Increased materialhandling therebymore exposure tometals residueslikely

Supervision 4 4 16

More. Process Emissions. More Vent gases.

Quenchingoperation

VOC.Residual reactants


Scrubber. 5 4 20

More. Fugitive Emissions Moreconcentration ofchemicals in workplace air


Receivers vents

Minor spills






Reverse Flow. Reverse flow ofair in system

Power failureduring recovery ofsolvent –Tolueneby distillation.

Ingress of air to hotflammable solventin the distillationsystem.


SOP.

Supervision.

3 3 9

54




As WellAs.

Effluent No Effluentgeneration inprocess of productno 95 howeverother productswill have processeffluent streams

Residual metalsalts likely to begoing in effluent

Unsafe condition ETP 4 4 16 Zinc , copper , Manganeseoxides ,lithium , Zicronium invarious compounds formslikely in effluent stream fromOrganometal products needattention for proper disposal

Other. Flow. Static charge. Static sensitiveSolvents lhandling.

Static charge assource of ignition,fire hazard.


3 3 9

Other Than. Flow Un intended mixup

Accidental mix up ,spill , floorwashings mix up indrain systemWrong valveoperationDyke failure etc.

Reactivity andcompatibilityhazards dependingupon thecompoundsinvolved .


4 4 16

More. Temperature. More temperature. Excessive heating. Emission at vent. TI.Supervision.

3 3 9 Provide temperature controllerfor steam line at hot watersystem.

Less. Temperature. Less temperature Excessive cooling. Not significant. – – –More. Pressure. More pressure. No Reaction

exothermNot significant System vented

through scrubber3 2 6 Provide SRV on the jacket of

the reactors handling solvents.

55









– – –

More.

Phase. More phases. Agitation loss (lossof power,mechanicalproblem etc.).

Disturbedoperation

SOP.

Supervision.

3 3 9

As WellAs.



3 3 9


DecompositionproductsFire conditions










SOP.

Supervision.

2 2 4

56




Other. Handling. solvents handling Fire /explosionhazardHealth hazard

Flameproofelectrical ,spark arrestors atvehicles exhaustStorage in secureand bounded area.Dyke for accidentalspill containmentfor above groundstorage tanksPortable fireextinguishers.Fire Hydrantsystem.Display of MSDS

4 4 16 Provision of PPE, SCBA.Warning signs.

Flame arrestor at tank vent.

Smoke detector ,

HC leak detector

Static charge control measures( earthing )Emergency procedures.

Ventilation.


57

NODE 8 OF 9 : Oxidation productsDESIGN INTENT : Manufacture of product Nootkatone , Oxidation generally means the addition of an electron-donating atom (such

as oxygen) and/or the removal of hydrogen to a compound.GuideWord Parameter Deviation Cause Consequence



No change inExistingcapacity of 0.4mt/m

No change Not significant - - -


More Vent gases.

Drowningoperation

Evoluation of gasin process

VOC.

More flow ofoxidising agentsuch as;PCC , TBHP


Scrubber. 5 4 20




Receivers vents

Minor spills







Not anticipated - - -

As WellAs.

Flow Effluentgeneration.

Aqueous layerprocess streamsat two steps


ETP provided. 3 3 9

58

NODE 8 OF 9 : Oxidation productsDESIGN INTENT : Manufacture of product Nootkatone

GuideWord






3 3 9

OtherThan.

Flow Un intendedmix up




4 4 16


Excessiveheating.

Emission atvent.

TI.Supervision.SRVInstrumentationRD

3 3 9 Establish the maximum safetemperature for exothermicreactions like Oxidation bycarrying out DSC test reviewthe Rupture Disc settingaccordingly.

Estimate the heat removedcapacity of the reactor atoperating conditions.Establish the maximum heatremoval requirement for thereaction system and hencethe safety margin available.


Excessivecooling.

Not significant. – – –

59


as oxygen) and/or the removal of hydrogen to a compound.

GuideWord



More. Pressure. More pressure. Reactionexotherm.


3 2 6 Provide SRV on thejacket of the reactors






– – –

More.

Phase. More phases. Agitation loss (lossof power,mechanicalproblem etc.).

Disturbedoperation

SOP.

Supervision.

3 3 9

As Well As. Composition Impurities . Impurities. environmentalissues.


3 3 9

OtherThan.


DecompositionproductsFire conditionsSide reactionproductsunreacted feed, by-productsOxidation reactionsmay produce tarsand ashes

Emissions ofvolatile organicsenvironmentalissues.

Careful control ofpartial oxidationreactions to preventthe material fromoxidising to agreater degree thandesired.


60


as oxygen) and/or the removal of hydrogen to a compound.

GuideWord









SOP.

Supervision.

2 2 4



Residue. Environmentalissues.


3 3 9

Other. Handling. Solventhandling

Iso octanehandling


Flameproofelectrical ,


4 4 16

Provision of PPE, SCBA.Warning signs.Static charge controlmeasures ( earthing )Emergency procedures.

Ventilation.

61

NODE 9 OF 9 : R & D productsDESIGN INTENT : R & D products ( intermediates)




No change inExistingcapacity of 0.4mt/m

No change Not significant - - -


More Vent gases.

DrowningoperationEvoluation of gasin process



Scrubber. 5 4 20 Provide scrubber atlaboratoryProvide leak detector atvent of the scrubber




Receivers vents

Minor spills







Power failureduring recoveryof solvent byvacuumdistillation.

Ingress of air tohot flammablesolvent in thedistillationsystem.


SOP.

Supervision.

3 3 9 Provide Nitrogen for breakingvacuum during solventrecovery by distillation.

62




As Well As. Effluentgeneration.

Mother liquorduringcrystallizationoperationsWashings.


ETP provided. 3 3 9

Other. Flow. Static charge. Static sensitivematerial handling.

Static charge assource of ignition,fire hazard.


3 3 9

Other Than. Flow Un intended mixup

Accidental mix up ,spill , floorwashings mix up indrain systemWrong valveoperationDyke failure etc.

Reactivity andcompatibilityhazards dependingupon thecompoundsinvolved .


4 4 16

More. Temperature. More temperature. Excessive heating. Emission at vent. TI.Supervision.

3 3 9 Provide temperature controllerfor steam line at hot watersystem.

Less. Temperature. Less temperature Excessive cooling. Not significant. – – –More. Pressure. More pressure. Reaction exotherm.

Faster addition ofcontrolled reactant.Excessive heatingwhen low boilingsolvent insidereactor.

Not significant System ventedthrough scrubber

3 2 6 Provide SRV on the jacket ofthe reactors handling lowboiling solvents.




– – –

63





Disturbedoperation

SOP.

Supervision.

3 3 9

As Well As. Composition Impurities . Impurities. environmentalissues.


3 3 9












SOP.

Supervision.

2 2 4



Spent catalyst.

Residue.



3 3 9

Handling. Corrosion. Acidic streams arecorrosive.


3 3 9

64




Other. Handling. solvents handling Flammablesolvents used


Flameproofelectrical ,

Portable fireextinguishers.Fire Hydrantsystem.Display of MSDSSafety shower andeye wash fountain

4 4 16 Provision of PPE, SCBA.Warning signs.

Flame arrestor at tank vent.

Smoke detector ,

HC leak detector

Static charge control measures( earthing )Emergency procedures.

Ventilation.


Other. Handling. Powders handling. Safety class of thepowder handlednot known.

Dust explosionhazard.

SOP.Supervision.Equipments areearthed.

3 3 9 Carry out dust safety tests andutilize the data whileequipment selection andoperation

65

SECTION 3 CONSEQUENCE ANALYSIS

3.1 INTRODUCTION

These accident scenarios as identified during HAZOP study are divided in twocategories considering the consequence seriousness and occurrence frequency.

MAXIMUM CREDIBLE LOSS SCENARIO (MCLS). WORST POSSIBLE SCENARIO.

MAXIMUM CREDIBLE LOSS SCENARIO (MCLS)

Maximum Credible Loss Scenario (MCLS) is one of the methodologies evolved toaccess the events in realistic and practical way. An MCLS can be described as theworst “credible” accident or as an accident with a maximum damage distance, whichis still believed to be probable. The analysis, however, does not include aquantification of the probability of occurrence of an accident. The MCLS aims atidentifying undesirable and hazardous events causing the Maximum damage to humanbeings environment around the industry under the consideration.

Leak from hose/ piping failure are quite probable events. Such accidental release isconsidered as MCLS.

WORST POSSIBLE SCENARIO

Worst Case Scenario/ MCA (Maximum Credible Accident) Accident Scenarioaccidental release of Hydrogen followed by fire/Explosion is considered as WorstCase Scenario/ MCA (Maximum Credible Accident).

HYDROGEN GAS INVENTORY & STORAGE

Hydrogen will be procured in a quad. A quad will have 20 cylinders eachhaving capacity of 29.6 cum hydrogegas ,160 ltrs w/c, with 200 kg /cm2filling pressure

There will be one stand by quad at hydrogenation plant

At a given time there will be 2 quad in the premises totalling to 1060 cum ofHydrogen gas (0.09MT).

66

3.2 CONSEQUENCE ANALYSIS

Accident scenario : release of hydrogen gasHydrogen Cylinder quad 1 no. , Met condition 1.5 , soft ware Phast

Radiation vs distance BLEVE Gas Cloud side view Flash fire

Table No. 3.1 A: Affect distance

Sr. Downwind Affect Distance (m)

No.Accident Scenario Toxic vapor cloud

Flammable

vapor cloud

LEL

PAC 3 PAC 2 PAC 1 IDLH 60 % 10 %

1 Hydrogen 2 no quad 125 163 277 - 524 1000

3 Meta Xylene <10 17 21 - <10 <10

4 Hydrogen chloride ERPG 3

16

ERPG 2

44

ERPG 1

115

- - -

Table No. 3.1 B : Affect distance

Sr. Downwind Affect Distance (m)

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

8 3.5 1.0 10 5 2

1 Hydrogen 90 Kg 441 449 498 <10 10 16

3 Meta Xylene - - - <10 <10 15

4 Hydrogen chloride - - - - - -

67

Hydrogen gas release –Dispersion PAC concentration

68

Hydrogen gas release –Flammable vapor cloud

69

HYDROGEN GAS RELEASE –VAPOR CLOUD EXPLOSION

70

M Xylene pool fire

71

SECTION 4 : IMPACT ASSESSMENT.

4.1 IMPACT ON LAYOUT

The Factory is established around 1960 . The present proposal will have direct positiveimpact on the site layout as it provides following oppertinuities

a) Optimization of inventory of hazardous chemicalsb) To rationalize the layout by relocating the solvent tank farm locations away from

HT power transmission lines .c) Ageing plant issues such as revamping damaged underground fire hydrant

network , revamping old electrical .d) Separation of bulk storages and segregation of laboratory chemicals considering

compatability and reactivity hazards .e) Separation of manufacturing facility by buffer green belt towards water body and

increased urbanzation pockets

4.2 OVER PRESSURE IMPACT

Hydrogen instantenous release from hydrogen cylinder quad followed by vapor cloudexplosion is considered as Worst case scenario

Table No. 4.1: Effect Of Blast Pressure Wave.OVER PRESSURE (bar) EFFECTS

0.01 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).

Vulnerable zone 1 up to 40 m radius from hydrogenation plant of 0.2068 bar over pressurevulnerable zone having the probability of 99 % fetality .Vulnerable zone 2 up to 52 m radius from hydrogenation plant of 0.1379 bar over pressurevulnerable zone having the probability of 10 % fetality .Vulnerable zone 3 up to 202 m radius from hydrogenation plant of 0.0206 bar overpressure vulnerable zone having the probability of 1 % fetality .

Table 4.2 : Availability of manpower in vulnerable zone

Block No Description Man powerG A B C Grand Total

23 library & quality control 26 2 2 2 3224 PP1 & Lab 2,4 31 8 7 5 5125 ADL LAB 4 0 1 1 626 hydrogenation plant & hydrogen gas cylinder storage 1 1 1 1 430 waste drum shed 0 0 0 0 0

Total Shift wise 62 11 11 9 93

72

There will be direct negative impact on the persons working in the vulnerable zone . risk of

affected by pressure wave as a result of Hydrogen Vapor cloud explosion is likely At first

shift change over Number persons likely to be present in the Hydrogenation plant and

vulnerable zone 1 and 2 will be 3 nos and 84 nos respectively . It should be noted that the

high density of Availability of manpower between 1 and 2 vulnerable zone is not desirable .

Depending the prevailing atmospheric conditions at the time of the event the impact will

under go change However any reduction in the crouding in this zone need attention .

4.3 THERMAL RADIATION IMPACT

Flammable solvent release followed Pool fire at tank farm will result in thermalradiations likely to impact direct the personnel in vulnerable zone with burn injuries andeven fetality .

Table no. 4.3: fatal thermal radiation exposure levels.RADIATION LEVEL

KW/m2SECONDS EXPOSURE FOR A % FATALITY LEVELS

1 % 50 % 99 %1.6 500 1300 32004.0 150 370 93012.5 30 80 20037.5 8 20 50

Table no. 4.4: 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.

73

4.5 TOXICITY IMPACT

Hydrogen chloride gas release at scrubber vent

HYDROGEN CHLORIDE

Hydrogen Chloride (HCl) is a colorless, corrosive, toxic gas with a pungent, irritating

odor. HCl is miscible in water. HCl is an irritant to eyes, skin, and mucous

membranes. HCl has a low threshold limit value (TLV) and is detectable by odor at

concentrations lower than those necessary to cause physical harm or impairment. The

most serious hazard presented by Hydrogen chloride is exposure to a large release

from which escape is impossible. Following Table describes various health effects of

Hydrogen Chloride exposure.

TABLE NO. 4.5: HEALTH EFFECTS OF HYDROGEN CHLORIDE EXPOSURE.

CONCENTRATION CONCENTRATION SYMPTOMS OF EXPOSURE< 1 ppm Odor Threshold.

10 - 50 ppm Irritation of the eyes and mucous membranes, which can betolerated or several hours.

50 - 100 ppm Immediate irritation of the throat, which may be tolerated foran hour.

1000 - 1300 ppm A dangerous health hazard, even for short periods of time.

NOTE: Exposure to concentrations in excess of 1300 ppm may cause laryngeal spasms,resulting in death.

Note 1 The potential consequences from the hazardous scenarios identified are determined and the impact zonesmodeled using ALOHA and PHAST software tools. The primary consequence types are pressure wave, thermalradiations and toxic gas release. The stable atmospheric stability conditions , ambient temperature of 30 oC,wind speed was 1.5 m/s. and humidity (50%) used for Consequence Analysis.

Note 2Apart from the maximum credible releases, the conservative approach appears in adoption of atmosphericconditions, used in the dispersion calculation. In general, the assumptions/ conditions will result in the largestdamage distances. Hence, it must be remembered that this analysis will be pessimistic & conservative inapproach & is only a planning tool. Its use should not be extended without understanding its limitations.

Note 3 . DISCLAIMER:Information contained in this report is believed to be reliable but no representation,guarantee or warranties of any kind are made as to its accuracy, suitability for a particular application or resultsto be obtained from them. It is up to the manufacturer to ensure that the information contained in the report isrelevant to the product manufactured/ handled or sold by him as the case may be. We make no warrantiesexpressed or implied in respect of the adequacy of this document for any particular purpose.

74

SECTION 5 FAILURE FREQUENCY ANALYSIS.

5.1 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.

5.2 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”.

5.3 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.

5.4 EVENT TREE

Event trees begin with an initiating event and work toward a final result. This

approach is inductive. The method provides information on how a failure can occur

and the probability of occurrence. Frequency of the incident is estimated by Event

Tree.

75

Hydrogen gas release

5.5 Ignition probability

*0.5 if distance to 50 % LFL falls within plant (with control of company) and *0.1 if distanceto 50 % LFL falls inside electrically classified area.

5.6 Initiating event frequency

Initiating event frequency/yr range (all causes included ) is 1 x 10-2 to 1x 10-3

Typical frequency values assigned to initiating events

Regular failure 1x10 -1

Gas kept/ packing blow out 1x10-2 yr Piping leak (10% sections), 100m 1x10-3/yr

Piping residual failure ,100m ,full breach 1x10-5 /yr Safety value opens spuriously 1x10-2 /yr

Operator failure (to execute routines procedure, well trained, unstressed, not fatigued)range 1 x 10-1 to 1 x 10-3/ opportunity

Raf: Table 11.3, Chemical process safety fundametals with apptications ; Dainel A Crowl /Joseph L.Second edition,

76

5.7 Review stage of Initiating event frequency

In the review meeting on draft QRA report on 8th July 2017 at Innovassynth Technologies

(I ) Pvt. Ltd. Site The Initiating event frequency was revised from 1 x 10 -2 to 1 x 10 -3 in

consideration of past safe operating expertise and maintenance of the hydrogenation facility

a )I n case initiating event frequency range (all causes included ) is 1 x 10-2 the estimated

Fire/ Explosion frequency becomes 4.4 x 10 -3 and 1,52 x 10 -3 for the above mentioned

ignition probibilities respectively

b) I n case initiating event frequency range (all causes included ) is 1 x 10-3 the estimated

Fire/ Explosion frequency becomes 4.4 x 10 -4 and 1,52 x 10 -4 for the above mentioned

ignition probibilities respectively

.

It is reasonable to assume this change however it should be noted it 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 to the original estimate (a )

indicated above .

TABLE 5.1 : EVENT FAILURE FREQUENCY( revised )

S.N. Event Event Frequency/ Yr1 Hydrogen gas accidental VCE 7.2 × 10-5

2 Hydrogen gas accidental flash fire 1.52 × 10-4

3 Flammable solvent (Methanol , Xylene) - pool fire. 1.0 × 10-4

4 Toxic gas release at scrubber vent. 1 × 10-3

77

SECTION 6 :RISK ESTIMATION.

6.1 INDIVIDUAL RISK

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

whereN = number of personsi Incident identification numberI, = impact of Incident ifi = frequency of the i incident

Average individual risk (exposed hours/worked hours) to personnel at periphery

of Hydrogenation plant is estimated at 2.37 x 10 -5

Table 6.1 : INDIVIDUAL FATALITY CRITERIA

RISK 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.

Table 6.2 : INDIVIDUAL RISK RESULTS*

Contour No. RiskDownwind

Affect Distance(M)

Remarks

1. 7.1 × 10-5 per year. 40 This contour remains within the site2. 7.2 × 10-6 per year. 52 This contour remains within the site3. 7.2 × 10-7 per year. 202 This contour remains within the site

ECC point is at approx 312 m away from the hydrogenation storage and not likely to

be affected due to this event .

TABLE 6.3 : SOCIETAL RISK

Sr.No.

Release eventNo. Offatality

Cumulativefrequency

1. Hydrogen- VCE 3 7.2 × 10-5

2 Hydrogen - flash fire - 2.2 × 10-4

3 Xylene -pool fire - 3.2 × 10-4

4 Hydrogen chloride

release

- 1.3 × 10-3

78

SECTION 7 : RISK MITIGATION MEASURES.

1 PP proposed to relocate Flammable solvent Tank farm from Block location no 19

near HT transmission line to proposed new tank farm .

2 Ensure any organic contaminated water generated during fire fighting operations,

sprinkler operation, accidental spill / floor washing at plant and parking locations not

entering storm drain or percolating in soil or water bodies.

3 Prepare SOP for vehicles, earthmoving machinery, cranes movements during

Demolition and construction activity near flameproof solvent storage / handling areas

and near HT transmission line.

4 Maintain hydrogen inventory up to 0.09 Mt.

5 Minimize or relocate manpower not connected with hydrogenation plant

manufacturing activity in the vulnerable zone.

6 Provide leak detector at the vent of Scrubber Sets used for Cyanation, Bromination

processes; Thionyl Chloride and POCL3 handling at plant PP3, 4, and 5. Also

provide closed charging arrangement of hazardous chemicals to reactor and leak

detector on shop floor .

7 Separate chemicals storage in bulk considering the compatibility and reactivity

hazards at tank farms, stores and warehouses. Segregate the laboratory chemicals

while storage on storage racks considering functional groups compatibility and

reactivity hazards .

8 A cyanide antidote kit should be kept in immediate work area and must be available

rapidly available.

9 Extend the fire hydrant network to the proposed installations.

79

10 Products (25 nos. ) are eliminated hence corresponding specific Raw materials for

those products will also be eliminated . Ensure safe disposal of such the left over

raw materials.

11 Zinc , copper , Manganese oxides ,lithium , Zirconium in various compounds forms

likely in effluent stream from Organometal products need attention for proper disposal

12 Disaster management plan: To address the residual risk issues a practical working

document DMP for site as per the format specified under "The the MSIHC Rules,

1989" is to be updated detailing Emergency organization , roles and responsibilities

and dove tailing information for offsite disaster control plan.

80

Annexure 1: Compatibility/ reactivity hazardPREDICTED HAZARDS REPORT--------------------------------------------------Chemicals and Reactive Groups in this Mixture:AMMONIUM HYDROXIDEBENZYL CHLORIDEBROMINEFORMALDEHYDE, SOLUTION, FLAMMABLEHYDROCHLORIC ACID, SOLUTIONN-BUTYL ALCOHOLTHIONYL CHLORIDE

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

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

BENZYL CHLORIDE mixed with AMMONIUM HYDROXIDE -PREDICTED HAZARDS:Reaction liberates gaseous products and may cause pressurizationReaction products may be corrosivePOTENTIAL GASES:Acid FumesHydrogen Halide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

BROMINE mixed with AMMONIUM HYDROXIDE -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 corrosiveReaction products may be explosive or sensitive to shock or frictionReaction products may be toxicPOTENTIAL GASES:Acid FumesAmmoniaChlorineChlorine DioxideHydrogen BromideHydrogen ChlorideHydrogen CyanideHydrogen FluorideHydrogen Halide

81

Hydrogen SulfideNitrogen OxidesOxygenSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

BROMINE mixed with BENZYL CHLORIDE -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 frictionReaction products may be toxicPOTENTIAL GASES:Halogen GasPhosgene--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

FORMALDEHYDE, SOLUTION, FLAMMABLE mixed with AMMONIUMHYDROXIDE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationPOTENTIAL GASES:Carbon Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

FORMALDEHYDE, SOLUTION, FLAMMABLE mixed with BENZYL CHLORIDE -PREDICTED HAZARDS:Reaction liberates gaseous products and may cause pressurizationReaction products may be corrosivePOTENTIAL GASES:Acid FumesHydrogen Halide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

FORMALDEHYDE, SOLUTION, FLAMMABLE mixed with BROMINE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Polymerization reaction may become intense and may cause pressurizationReaction liberates gaseous products and may cause pressurizationReaction may be particularly intense, violent, or explosiveReaction products may be corrosiveReaction products may be explosive or sensitive to shock or frictionReaction products may be flammable

82

Reaction products may be toxicPOTENTIAL GASES:Acid FumesAcid HalideCarbon DioxideCarbon MonoxideChlorineChlorine DioxideHydrogenHydrogen BromideHydrogen ChlorideHydrogen CyanideHydrogen FluorideHydrogen HalideHydrogen SulfideNitrogen OxidesOxygenPhosgeneSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

HYDROCHLORIC ACID, SOLUTION mixed with AMMONIUM HYDROXIDE -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 corrosivePOTENTIAL GASES:Acid Fumes--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

HYDROCHLORIC ACID, SOLUTION mixed with BENZYL CHLORIDE -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 corrosiveReaction products may be toxicPOTENTIAL GASES:Acid FumesHydrogen Halide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

HYDROCHLORIC ACID, SOLUTION mixed with BROMINE -PREDICTED HAZARDS:

83

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 corrosiveReaction products may be explosive or sensitive to shock or frictionReaction products may be flammableReaction products may be toxicPOTENTIAL GASES:Acid FumesBromineChlorineChlorine DioxideHalogen GasHalogen OxidesHydrogen BromideHydrogen ChlorideHydrogen CyanideHydrogen FluorideHydrogen HalideHydrogen SulfideNitrogen OxidesOxygenSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

HYDROCHLORIC ACID, SOLUTION mixed with FORMALDEHYDE, SOLUTION,FLAMMABLE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Polymerization reaction may become intense and may cause pressurizationReaction liberates gaseous products and may cause pressurizationReaction products may be corrosivePOTENTIAL GASES:Acid Fumes--- 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 ---

N-BUTYL ALCOHOL mixed with AMMONIUM HYDROXIDE -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N-BUTYL ALCOHOL mixed with BENZYL CHLORIDE -PREDICTED HAZARDS:

84

No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N-BUTYL ALCOHOL mixed with BROMINE -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 corrosiveReaction products may be explosive or sensitive to shock or frictionReaction products may be flammableReaction products may be toxicPOTENTIAL GASES:Carbon DioxideCarbon MonoxideHalogen GasHalogen OxidesHydrogenHydrogen Halide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N-BUTYL ALCOHOL mixed with FORMALDEHYDE, SOLUTION, FLAMMABLE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction may be particularly intense, violent, or explosivePOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

N-BUTYL ALCOHOL 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 ---

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

THIONYL CHLORIDE mixed with AMMONIUM HYDROXIDE -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 corrosiveReaction products may be toxic

85

POTENTIAL GASES:Acid FumesCarbon DioxideHydrogen ChlorideHydrogen FluorideHydrogen HalideHydrogen IodideHydrogen SulfateHydrogen SulfideSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

THIONYL CHLORIDE mixed with BROMINE -PREDICTED HAZARDS:Exothermic reaction at ambient temperatures (releases heat)Reaction liberates gaseous products and may cause pressurizationReaction products may be corrosiveReaction products may be toxicPOTENTIAL GASES:Halogen GasNitrogen Oxides--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

THIONYL CHLORIDE mixed with FORMALDEHYDE, SOLUTION, FLAMMABLE -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 corrosiveReaction products may be toxicPOTENTIAL GASES:Acid FumesCarbon DioxideHydrogen ChlorideHydrogen FluorideHydrogen HalideHydrogen IodideHydrogen SulfateHydrogen SulfideSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

THIONYL CHLORIDE mixed with HYDROCHLORIC ACID, SOLUTION -

86

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 corrosiveReaction products may be toxicReaction products may be unstable above ambient temperaturesPOTENTIAL GASES:Acid FumesCarbon DioxideHydrogen ChlorideHydrogen FluorideHydrogen HalideHydrogen IodideHydrogen SulfateHydrogen SulfideSulfur Dioxide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

THIONYL CHLORIDE mixed with N-BUTYL ALCOHOL -PREDICTED HAZARDS:Reaction liberates gaseous products and may cause pressurizationReaction may be particularly intense, violent, or explosiveReaction products may be corrosiveReaction products may be flammableReaction products may be toxicPOTENTIAL GASES:Acid FumesHydrogen Halide--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

87

Annexure 2: Mond index assessment worksheets

99

Annexure 3: Dow F & E index.DOW FIRE & EXPLOSION INDEX worksheet.PLANT: HYDROGEN CYLINDER SHED.MATERIALS AND PROCESS: HYDROGEN.MATERIAL FACTOR: 21

PENALTYFACTORRANGE

PENALTYFACTOR USED

1. GENERAL PROCESS HAZARDSBase Factor. 1.0 1.0A. 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 0.5D. 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 0.0General Process Hazards Factor (F1). 1.5

2. SPECIAL PROCESS HAZARDSBase Factor. 1.0 1.0A. Toxic Materials. 0.20 to 0.80 0.0B. 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 0.33. Always in Flammable Range. – –

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

90 Kgs , 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 00Special 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 LightRADIUS OF EXPOSURE 15 meterDAMAGE FACTOR 0.58

100

DOW FIRE & EXPLOSION INDEX worksheet.PLANT: Solvent Tank farm (35)MATERIALS AND PROCESS: Meta xyleneMATERIAL FACTOR: 16

PENALTYFACTORRANGE

PENALTYFACTOR USED

1. GENERAL PROCESS HAZARDSBase Factor. 1.0 1.0A. 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 0.5D. 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 0.0General Process Hazards Factor (F1). 15

2. SPECIAL PROCESS HAZARDSBase Factor. 1.0 1.0A. Toxic Materials. 0.20 to 0.80 0.4B. 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 – 00F. Low Temperature. 0.20 to 0.50 00G. Quantity of Flammable/ Unstable Material

45 kl Kgs , Hc 17.6 103 BTU/Lb.– –

1. Liquid or Gases in Process. – –2. Liquid or gases in Storage. – 0.323. 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 00Special Process Hazards Factor (F2) 1.92

Unit Hazards Factor (F1 F2 = F3). 2.88Fire and Explosion Index (F3 MF) (F & IE). 46THE DEGREE OF HAZARD LightRADIUS OF EXPOSURE 10.5 meterDAMAGE FACTOR 0.39T = {125 +50×(1 + 1.5 + 1.92)}/100 =3.46 T Category I

101

DOW FIRE & EXPLOSION INDEX worksheet.PLANT: Solvent Tank farm (19)MATERIALS AND PROCESS: MethanolMATERIAL FACTOR: 16

PENALTYFACTORRANGE

PENALTYFACTOR USED

1. GENERAL PROCESS HAZARDS.Base Factor. 1.0 1.0A. 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 0.25D. 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 0.0General Process Hazards Factor (F1). – 1.25

2. SPECIAL PROCESS HAZARDS.Base Factor. 1.0 1.0A. Toxic Materials. 0.20 to 0.80 0.2B. 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 00F. Low Temperature. 0.20 to 0.50 00G. Quantity of Flammable/ Unstable Material

34.25 kl , Hc 8.6 103 BTU/Lb.– –


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 00Special Process Hazards Factor (F2) – 1.72

Unit Hazards Factor (F1 F2 = F3). 2.15Fire and Explosion Index (F3 MF) (F & IE). 34THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 8.7 meterDAMAGE FACTOR. 0.26T = {50 +50×(1 + 1.25 + 1.72)}/100 =2.48 T Category I

102

DOW FIRE & EXPLOSION INDEX WORKSHEETPLANT: TANK FARM.MATERIALS AND PROCESS: FURNACE OIL.MATERIAL FACTOR: 10.

PENALTYFACTORRANGE

PENALTYFACTOR USED

1. GENERAL PROCESS HAZARDSBase Factor. 1.0 1.0A. Exothermic Chemical Reactions. 0.30 to 1.25 0.0B. Endothermic Process. 0.20 to 0.40 0.0C. Material Handling & Transfer. 0.25 to 1.05 0.2D. Enclosed or Indoor Process Unit. 0.25 to 0.90 0.0E. Access. 0.20 to 0.35 0.0F. Drainage and Spill Control. 0.25 to 0.50 0.0General Process Hazards Factor (F1). 1.2

2. SPECIAL PROCESS HAZARDSBase Factor. 1.0 1.0A. Toxic Materials. 0.20 to 0.80 0.0B. Sub – Atmospheric Pressure. 0.50 0.0C. 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. – 0.0

D. Dust Explosion. 0.25 to 2.0 0.0E. Pressure Operating atmospheric; 1.7 × 0.7. – 0.12F. Low Temperature. 0.20 to 0.50 0.0G. Quantity of Flammable/ Unstable Material

10 Kl Hc 18.7 103 BTU/Lb.– –


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. – 0.0K. Hot Oil Heat Exchange system > 210 ft. 0.15 to 1.15 0.0L. Rotating Equipment. 0.5 0.0Special Process Hazards Factor (F2) 1.45

Unit Hazards Factor (F1 F2 = F3). 1.74Fire and Explosion Index (F3 MF) (F & IE). 17.4THE DEGREE OF HAZARD LIGHT.RADIUS OF EXPOSURE 4.5 meter.DAMAGE FACTOR 0.11

103

Annexure 4 : Preliminary hazard analysisPhase of the project

Sr.no.

Hazard

Pre

Con

stru

ctio

n

Con

stru

ctio

n

Ope

rati

on

Pos

t Ope

rati

on /

Dec

omm

issi

onin

g

Nat

ural

Cau

ses

Cyclone √ √ √Earth quake √ √ √Land slide √ √ √Flooding - heavy rain , √ √ √

Phy

sica

l haz

ards

Noise √ √ √Radiation (UV , radioactive materials ) x x X X

Extreme temperatures √ √ √Vibration √ √ √Material handling operations. √ √ √Steam pressure piping failure/ boiler drum failure. √Boiler explosion. √

Bio

haza

rds Epidemics /Communicable diseases by pests ,insects

,rodents√ √ √

Animal / snake bites √ √ √Occupational health hazards at industry √ √

Ele

ctri

cal

haza

rd

Transformer oil fire /explosion √ √ √Lightening strike √ √ √ √fires due to Short circuit √ √ √Power outage √ √ √

Haz

ardo

us s

ubst

ance

s an

dw

aste

s

AC , Refrigerators , Air conditioners Units fire/ explosion √ √Diesel fire at DG set √ √ √Foul odor at dumping sites √ √ √Hazardous waste uncontrolled disposal √ √ √Flammable chemicals- fire /explosion √ √ √Gas cylinders failure -fire /explosion √ √ √ √Release of toxic gas √Site decontamination x x x XSmoke in fire , acrid gases in fire , dumping yard √ √Vehicles fuel fire √ √ √ √

Mec

hani

cal

Failure of machinery and equipment √ √ √Lack of safety guards in machines √ √ √Poor maintenance of machinery and equipment √ √ √power driven tools , saws , grinders ,d abrasive cuttingwheels

√ √ √

scaffolding –fixed and portable failure √ √ √structural failure √ √ √Truck and transport vehicles √ √ √

104

IDENTIFICATION OF HAZARD. check list Phase of the projectSr.no.

Hazard

Pre

Con

stru

ctio

n

Con

stru

ctio

n

Ope

rati

on

Pos

t Ope

rati

on /

Dec

omm

issi

onin

g

Sto

rage

s &

proc

ess

oper

atio

ns

Spill xylene at parking lot √ √tank pressurization / failure √ √Static charge as source of ignition √ √Hydrogen release at hydrogenation plant √ √Compatability and reactivity hazard at chemical store √ √Fire at dyke/ at tank. √ √

Fre

quen

t cau

ses

of a

ccid

ents

dur

ing

cons

truc

tion

Act

ivit

y

Being struck by falling object √ √ √Caught in or compressed √ √ √Cranes , winches , hoisting and hauling equipments failure √ √ √Dusting √ √ √Electricity ( electrocution ) √ √ √Fall from height, √ √ √uncontrolled explosion during demolition / landdevelopment

√ √

Hit by sharp objects √ √Injuries during Handling heavy objects √ √Lack of PPE , housekeeping practices , safety signs √ √ √Oxygen deficiency in confined spaces √ √Paint/ thinner cleaners, pesticides , waste oil , flammablecombustible materials fire at store

√ √ √

Poor illumination √ √ √Slipping on wet surfaces √ √Snapping cables , ropes , chains , slings , hooks , chains √ √ √Struck by moving objects √ √ √ √Welding fumes and Radiations √ √

Erg

onom

ics

&ps

ycho

soci

alha

zard

s

Repetitive ,monotonous ,excessive workload , strain injuries √ √Mental stress , human relations ( aggressive behavior ,alcohol and drug abuse , violance )

√ √ √

Poverty , low wages , lack of education √ √ √Long working hours , shift work , temporary employment √ √ √Security threats

Oth

er

Escalating the designed event during MOCK drill √ √ √Power outage to emergency equipments /power cablefailure

√ √ √

Stampede during evacuation /at assembly point √ √ √Spreading Rumors √ √ √ √Shortage of fire water supply √ √ √

105

ANNEXURE 5 : GLOSSARY

AcceptanceCriteria (Risk).

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

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

ERPG : The Emergency Response Planning Guidelines.ERPG 1: The maximum airborne concentration below which it is believed that nearlyall individuals could be exposed for up to 1 hour without experiencing other than mildtransient adverse health effects or perceiving a clearly defined, objectionable odor.ERPG 2: The maximum airborne concentration below which it is believed that nearlyall individuals could be exposed for up to 1 hour without experiencing or developingirreversible or other serious health effects or symptoms which could impair anindividual's ability to take protective action.ERPG 3: The maximum airborne concentration below which it is believed that nearlyall individuals could be exposed for up to 1 hour without experiencing or developinglife-threatening health effects.

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

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

HazardousScenario

: The identified isolatable sections and/or those which have been broken down intoscenarios for specific items of equipment.

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

Individual Risk : The frequency at which an individual may be expected to sustain a given level of harmfrom the realization of specified hazards.

Individual RiskContours.

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

Individual RiskOf Fatality.

: Individual risk with “harm” measured in terms of fatality. It is calculated at a particularpoint for a stationary, unprotected person for 24 hours per day, 365 days per year.Normally measured in chances of fatality per million years.

Individual RiskOf Injury.

: Similar to individual risk of fatality, however with “harm” measured in terms of injury.

106

Isolatable Section. : A system of pipes or vessels containing the hazardous materials that are bounded byspecific isolation points.

Isolation Point. : A point in the process, which can be used to isolate one part of the process from therest of the system.

LEL. : Lower Flammability Limit.Expressed as % by volume of flammable gas in air. This is the minimum concentrationof gas in air mixture which can ignite. Gas air mixtures below this concentration donot ignite.

Probability. : The expression for the likelihood of an occurrence of an event or an event sequence orthe likelihood of the success or failure of an event on test or demand. By definition,probability must be expressed as a number between 0 and 1.

QuantitativeRisk Assessment.

: A risk assessment undertaken by combining quantitative evaluations of eventfrequency and consequence.

Risk. : The combination of frequency and consequences, the chance of an event happeningthat can cause specific consequences.

Risk Reduction. : The process of risk assessment coupled to a systematic consideration of potentialcontrol measures and a judgment on whether they are reasonably practicable toimplement.

TEEL : Temporary Emergency Exposure Limits.TEEL-1: Maximum concentration in air below which it is believed nearly allindividuals could be exposed without experiencing other than mild transient healtheffects or perceiving a clearly defined objectionable odor.

TEEL-2: Maximum concentration in air below which it is believed nearly allindividuals could be exposed without experiencing or developing irreversible or otherserious health effects or symptoms that could impair their abilities to take protectiveaction.

TEEL-3: Maximum concentration in air below which it is believed nearly allindividuals could be exposed without experiencing or developing life-threateninghealth effects.

UFL : Upper Flammability Limit.Expressed as % by volume of flammable gas in air. This is the maximumconcentration of gas in air mixture which can ignite. Gas air mixtures above thisconcentration do not ignite.

Vapor CloudExplosion

: An accidental release of flammable liquid or gas, there is possibility that it may form acloud which can spread along the wind direction. Delayed ignition of the cloud awayfrom the source of release results in Vapor cloud explosion (flash back) and associatedblast/ over pressure effects.

107

ANNEXURE 6: ABBREVIATIONSAIChE. 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.

108

ANNEXURE 7: REFERENCES

1. Technical EIA Guidance Manual for Synthetic Organic Chemicals, prepared for 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. Chemical process safety fundametals with apptications ; Dainel A Crowl / JosephL.Second edition,

9. Guideline for Quantitative Risk Assessment “Purple Book”.

109

Please make following corrections in QRA report and revert back as early as possible,

risk assessment -...

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