Inventys Hazop Final 100 -...

HAZOP STUDY

PROPOSED EXPANSION PROJECT

Tà

Inventys Research Company Pvt. Ltd. PLOT NO. K – 38, MIDC INDUSTRIAL AREA, BUTIBORI, VILLAGE: KIRMITI, TALUKA: HIGADA, DISTRICT: NAGPUR, MAHARASHTRA.

APRIL 2014

2

CONTENTS

SECTION DESCRIPTION PAGE NO.

1. EXECUTIVE SUMMARY. 03

2. INTRODUCTION. 11

3. IDENTIFICATION OF HAZARDS 21

Node 1 Tank Farm. 22

1.1 Acetic Acid. 231.2 Acetone. 271.3 Hydrogen Peroxide. 311.4 Hydrochloric Acid. 361.5 Phenol. 381.6 Tetra Hydro Furan. 421.7 Toluene. 46

Node 2 Halogenation. 50

2.1 Chlorine handling. 522.2 Bromine. 592.3 Process Operations. 612.4 Vent Scrubber. 66

Node 3 Hydrogenation. 71

Node 4 Oxidation. 76

Node 5 Hydrolysis. 81

Node 6 Distillation. 85

Node 7 Others. 88

ANNEXURE 1 COMPATIBILITY/ REACTIVITY HAZARDS. 93

ANNEXURE 2 HAZOP METHODOLOGY. 100

ANNEXURE 3 MSDS – HIGHLIGHTS. 107

3

SECTION 1: EXECUTIVE SUMMARY

1.1 INTRODUCTION

M/s. Inventys Research Company Pvt. Ltd., (Inventys) is located at Plot No. K – 38,

MIDC Industrial Area, Butibori, Village: Kirmiti, Taluka: Higana, District: Nagpur,

Maharashtra. The total plot area is 28,327 Sq.M. out of which 3,430 Sq. M. has been

occupied by the existing activity for manufacturing 420 MT/year of products.

The present proposal is for Expansion & New Project in existing plot for

manufacturing Agrochemicals/ Pesticides, Bio - Pharmaceuticals, Advanced

Intermediates for Pharma Industry, API, Fine chemicals and specialty chemicals. The

Maximum magnitude of operation will be 11,400 MT/ Yr. of products including

present activity and 2105 MT/Yr. By-products including present.

1.2 THE ASSIGNMENT

1.2.1 As per the EIA notification SO 1533 issued on 14th September 2006, the

proposal by Inventys Research Company private limited is classified as 5(b),

5(f) of schedule. It falls under category “A” as Agrochemicals/ Pesticides 5(b)

is in “A” category and 5(f) Synthetic Organic Chemicals is in “B” category.

The EIA study has been conducted Goldfinch Engineering Systems Pvt. Ltd.

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

Functional Expert – Risk Assessment and Hazard Management (RH)”

associated with M/s. Goldfinch Engineering Systems Pvt. Ltd. Mr. S. L.

Bonde undertook this study in compliance of above requirements.

1.2.3 The present report is part of the QRA report for the proposed manufacturing

facility and prepared towards compliance to above requirements.

1.3 HAZOP STUDY METHODOLOGY

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

procedures that recognize and eliminate potential problems in the design stage.

Hazard Operability study is now used to great satisfaction throughout the

chemical industries.

4

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

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

preliminary process design flow sheet at the start of a project or detailed

piping and instrument diagrams at the final design phase and during

modifications of the existing plants.

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

principle that a problem can only arise when there is a deviation from what is

normally expected. The procedure, therefore, is to search the proposed scheme

systematically for every conceivable deviation, and then look backwards for

possible causes and forwards for the possible consequences.

1.3.4 HAZOP COMMITTEE

Chairman Dr. Shrikant Sakhalkar. President.

Co-Ordinator Mr. S. R. Kanade. Dy. Works Manager.

Mr. Shrihari Athavale. EIA Co – Ordinator.

Member Mr. Girish Rage. V. P. – Operations.

Mr. Shrinivas Holennavar. Works Manager.

Mr. Anil Mehra. Asst. General Manager.

Mr. N. S. Dhande. Plant Manager.

Moderator Mr. Subhash Bonde. EIA Functional Area Expert- RH

1.3.5 HAZARD RATING METHODOLOGY

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

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

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

5

HAZARD PROBABILITY & SEVERITY RATING.

Hazard Probability Value Hazard Severity Value

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

HAZARD RATING

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

ratings between 1 and 25 is obtained.

HAZARD RATING MATRIX.

SEVERITY

PROB

ABIL

ITY

Very High.

5 High.

4 Moderate.

3 Slight.

2 Nil. 1

Very Likely. 5

25 20 15 10 05

Likely. 4

20 16 12 08 04

Quite Possible. 3

15 12 09 06 03

Possible. 2

10 08 06 04 02

Not Likely. 1

05 04 03 02 01

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

evaluate it according to the following.

• Urgent situations (20 to 25) that require action

immediately.

• High-risk situations (10 to 16) that require action in the

short and medium-term.

• Medium-risk situations (5 to 9) that require action or

further evaluation within an appropriate period.

• Low-risk situations (less than 5) that may require

relatively little or no action.

Step 5: : Decide on the priorities for action and allocate resources to

areas where they are likely to have the greatest impact.

6

1.4 NODES

1.4.1 List of products is given in following table. All the products are

studied under 9 nodes based on unit processes and operations

involving or likely to involve one or more hazardous chemicals as

listed under Schedule – 4 [see Rule 2(c), 2(e)] “The Manufacture

Storage Import Hazardous Chemical Rules, 1989”.

1.4.2 FINISHED PRODUCTS

LIST OF PRODUCTS AND BY-PRODUCTS

SR. NO. PRODUCT NAME

CAPACITY (Mt./year). EXISTING PROPOSED

1. Advanced intermediates. 420 2550 1 s Methyl Phenyl Glycine Methyl

Ester (sMPGM). (180) (600)

2 Methyl 5 Phenyl Imidazolidine 2,4-dione (rMPID).

(240) (900)

Others: 82 nos. – (1050) 2. Bulk intermediates. 6 nos. Nil 6000 3. Perfumery & cosmetics. 18 nos. Nil 450 4. Pesticides. 5 nos. Nil 800 5. API’s. 118 nos. Nil 1200 6. API Intermediate. 28 nos. Nil 400 TOTAL 420 11400

As the production plan will solely be depending on the customer requirement

and market demand, multipurpose manufacturing plants have been envisaged

and a large number of products have been incorporated in the product list.

However, maximum 10 Nos. of products will be simultaneously produced at

any given time in this multipurpose facility.

1.4.3 UNIT PROCESS AND UNIT OPERATIONS

PRODUCT (TYPICAL) API

Advance Intermediate

Pesticide Bulk

IntermediateUNIT PROCESSES 1 2 3 4 5 6 7 8 9 Halogenation* – – – – – – – – Hydrogenation* – – – – – – – – Oxidation * – – – – – – – – Hydrolysis* – – – – – – – – Others –

7

Where; Product 1: Montelukast. Product 2: Rivastigmine tartrate. Product 3: Tamoxifen Citrate. Product 4: 1,8-Octanediol. Product 5: Delta Deca Lactone. Product 6: 3-Cyano quinoline. Product 7: Azoxystrobin. Product 8: Acetonitrile. Product 9: m-Phenoxy benzaldehyde.

In addition unit operations such as follows are involved in the site operations.

1. Absorption. 9. Drying. 17. Phase Separation. 2. Adsorption. 10. Evaporation. 18. Precipitation. 3. Apparatus Cleaning. 11. Extraction.* 19. Product Washing. 4. Centrifugation. 12. Filtration. 20. Quenching. 5. Charging Reactants & Solvents. 13. Fractionation. 21. Separation. 6. Crystallisation. 14. Inerting. 22. Stripping. 7. Discharging. 15. Milling. 23. Ultra Filtration. 8. Distillation.* 16. Mixing.* 24. Charcoal Treatment. *Unit processes and operations involving or likely to involve one or more hazardous chemicals as listed under SCHEDULE – 4 [See Rule 2(c), 2(e)] “The Manufacture Storage Import Hazardous Chemical Rules, 1989”.

1.5 REACTIVITY/ COMPATIBILITY HAZARDS MATRIX (TYPICAL)

CHEMICAL (1) (2) (3) (4) (5) (6) (7) 1. Acetone. C. A5, A6,

B4, C, D3, E, G.

2. Tetra Hydro Furan.

A6, B5, C, D3, D7, E.

A2, A6, A8, B4, C, D3.

3. Toluene. A3, B4, C, D4, E.

4. Acetic Acid, Glacial.

B6, C, D7.

A5, A6, A8, B4, B6, C, D5, E.

5. Hydrochloric Acid, Solution.

C. A6, B5, C, D3, D7, E.

B6, C, D7.

C, D7. A9, B4, C, D3, D5, D6, D7, G.

6. Phenol, Liquid. C, D7 B1, B6, C 7. Hydrogen Per

Oxide, Stabilized.

A5, A6, B4, C, D3, E, G.

A2, A6, A8, B4, C, D3.

A3, B4, C, D4, E.

A5, A6, A8, B4, B6, C, D5, E.

A9, B4, C, D3, D5, D6, D7, G.

B1, B6, C.

8

A2 Risk of explosion by shock, friction, fire or other sources of ignition. A3 Forms very unstable explosive metallic compounds. A5 A6 Reaction proceeds with explosive violence and/or forms explosive products. A8 Explosive when mixed with combustible material. A9 Heat generated from chemical reaction may initiate explosion.

B1 May become highly flammable or may initiate a fire, especially if other combustible materials are present.

B4 Spontaneous ignition of reactants or products due to reaction heat. B5 B6 Combination liberates gaseous products, including both flammable and toxic gases.

May cause pressurization.

C Exothermic reaction, may generate heat and /or cause pressurization.

D3 Combination liberates gaseous products, at least one of which is toxic. May cause pressurization.

D4 D5 Combination liberates combustion-enhancing gas (e.g., oxygen). May cause

pressurization. D6 Exothermic, generation of toxic and corrosive fumes. D7 Generation of corrosive liquid.

E Generates water soluble toxic products.

G Reaction may be intense or violent.

1.6 MODES

Mode of operation is batch wise for all the products.

1.7 HAZOP WORKSHEET

HAZOP worksheets are enclosed under respective NODE Sections. Thrust area of the

study is on environmental issues in the proposed manufacturing activity.

1.8 HAZARDOUS EVENTS

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

environmental issues in the porposed activities. Total Seven Nodes are studies and

out of the 246 number of hazardous events identified 20 number events are identified

as MCA (Maximum Credible Accident having risk rating 20 to 25 range). These

events are summerised (excluding repetation) as follows;

9

STORAGE AND HANDLING

Toxic gas release at cylinder storage.

Fire/ explosion hazard at cylinder storage.

Spill/ fire/ explosion hazard at flammable solvent storage.

Reactivity/ compatibility hazards due to large number of chemicals.

PROCESS OPERATIONS

Explosion hazard at reactor due to uncontrolled exothermic reactions.

Health hazard due to vapors emissions at work place.

Toxic gas release at vent in case of scrubber failure.

Fire explosion hazard due to Static charge as source of ignition in handling of

solvents.

These events have potential of fire/ explosion/ toxic gas release, hence based on this

exercise following accident scenarios are considered for Consequence Analysis.

Toxic gas release.

Spill of flammable solvent followed by fire/explosion.

Fire/ explosion at flammable gas cylinder.

1.9 We thank the staff and the Management for positive approach shown and excellent

co-operation extended through out the studies to complete the studies in scheduled

time frame.

10

SECTION 2: INTRODUCTION

The present proposal is for Expansion & New Project in existing plot for manufacturing

Agrochemicals/ Pesticides, Bio - Pharmaceuticals, Advanced Intermediates for Pharma

Industry, API, Fine chemicals and specialty chemicals. The Maximum magnitude of

operation will be 11,400 MT/ Yr. of products including present activity and 2105 MT/Yr. By-

products including present.

Inventys has already manufacturing a specialty chemical in the existing manufacturing area.

With this strong background and experience, Inventys is planning to put 8 GMP plants of

specialty chemicals. These plants will be of three storied. Each plant is assigned to

manufacture specialty chemicals/ API/ Fine chemicals/ Bio Pharmaceuticals/ Perfumery

chemicals/ Chemicals for other industries. The planned reaction capacity per plant is ~150-

200 Kl.

List of some of the important processes that are considered in plant design are:

Conversion of acid to the corresponding nitriles. Alternately some of the products

can be based on ammoxidation.

Alkylation.

Hydrogenations (continuous including high pressure).

Acetone based product.

Oxidation.

Ketones from Carboxylic Acids.

Etherification of Phenolics.

Glycidisation (Reaction of aromatics/ Aliphatic alcohols with epichlorohydrin).

Specialty bisphenols (condensation of Phenols with ketones).

Amination.

As the production plan will solely be depending on the customer requirement and market

demand, multipurpose manufacturing plants have been envisaged and a large number of

products have been incorporated in the product list. However, maximum 10 Nos. of products

will be simultaneously produced at any given time in this multipurpose facility.

11

RAW MATERIALS

SN NAME OF RAW MATERIAL SN NAME OF RAW MATERIAL 1 Cyclohexane 43 2-dimethylamino ethyl chloride 2 ( R ) --2-4-Methoxy 3 amino sulfophenyl 1 methyl

ethylamine 44 3,3-dimethoxy-2-formyl-propanenitrile sodium

3 (s)-(-) 2,6 diamino 4,5,6,7- tetrahydrobenzothazile ( 9 gm )

45 2S, 3S, 6S octahydro cyclo penta pyyrrole 2 carboxylate acid

4 1 benzyl 4, 5-6 dimethoxy 1 oxo indan-2-ylidine methyl piperidine

46 3-(dimethyl amino) 1-(3-pyridinyl)-2- propene-1-one (C10H12N2O)

5 2,3,5-tri-o-benzyl-1-o-p-nitrobenzoyl-D-arabino furanose ( C33H31NO8 )

47 3,4 dihydro 6 methyl 4 phenyl 2H benzoran 2 ol

6 2-Nitrobenzaldehyde 48 3,4 Dihydroxy 5 nitro benzaldehyde 7 3-dimethyl malonyl-2-pentylcyclopent-1-one 49 4 hydroxy 2 methyl 2H 1,2 benzothiozine 1,1 dioxide 3

carboxylic acid methyl ester 8 55-65% sodium hydride 50 4,6-dichloro pyridine ( C4H2CL2N2 ) 9 6- ( 5-chloropyridzyl), 5,7 dioxo,6,7, dihydro-5H Pyrole (

3,4 b) pyrazine 51 4-2 dipropylaminoethyl indole

10 alpha cyclohexyl phenyl glycolic acid propanyl ester 52 4-chloro carbonyl 4 methyl piperazine 11 B, B - Dichloro ethyl ether 53 4-Methoxyphenyl Acetone 12 dry dimethylsulfoxide 54 4-Methyl Phenacyl bromide 13 Ethyl vinyl ether 55 4-methyl-2-pentanone 14 Guanidine 56 5%- Palladium on carbon 15 Imidazol 4 y acetic acid 57 5,5-Dimethyl hydantoin 16 methyl 2, 2,3 dichloro benzylidine acetoacetate 58 5-chloro-1,3-dihydro-l-(4-piperidinyl)-2H-benzimidazol-

2- one

17 methyl iodide 59 5-o-trityl 2,3 amhydrothymidine 18 N,N Diethyl cyanoacetamide 60 7 Chloro 1 cyclopropyl 6 fluoro 1 4 dihydro 4 oxyquinitine

3 carboxylic acid 19 O,N-dibenzyloxycarbonyl-des-Nmethylerythromycin A 61 7-Chloro-Guinaldehyde 20 Trans 6,6 dimethyl hept 2-ene-4 ynyl 1bromide 62 â-Aminocrotonic acid methyl ester 21 trifluoro acetic anhydride 63 Acetic Acid 22 1- P Beta dimethylamino phenoxy phenyl )-1,2-diphenyl

butan-1-ol 64 Acetic anhydride

23 1-(3-chloropropyl)-1,3-dihydro-2H-benzimidazol-2-one 65 Acetoacetic acid methyl ester 24 1,2 benroxazole 3 methane sulfonyl chloride 66 Acetoacetic acid N-benzyl-N-methylaminoethyl ester 25 10 % Sodium bicarbonate soln(NaHCO3) 67 Acetone 26 1-2 cyanobiphenyl 4 yl methyl ammocarbonyl pentanoyl

amino cyclopentane 68 Acetonitrile

27 1-2S 3 acetyl thio 2 methyl propanoyl L Proline 69 Acetophenone 28 1-thio methyl Cyclopropane acetic acid 70 Adipic acid 29 2 amino 5 methyl pyridine 71 AlCl3 30 2 amino pyridine 72 Ammonia 31 2 chloro 3, 4 dihydroxy acetophenone 73 Ammonium acetate 32 2 chloro pyridine N Oxide 74 Ammonium carbonate 33 2 ethoxy phenoxy ethyl bromide 75 Anhydrous CalCl2. 34 2 methyl - 5 nitro benzene amine (C7H8N2O2) 76 Aniline 35 2 s 1 chloro carbonyl ethylamino 4 phenyl butanoate HCl 77 Benzaldehyde 36 2-(2-hydroxyphenyl)-3- methoxy propeonic acid methyl

ester ( C11H1204 ) 78 Benzene

37 2,3 dioacetyl 5 deoxy 5 fluro cytidine 79 Benzene sulfonyl chloride 38 2,3 xylidine 80 Benzophenone 39 2,4,5,6 Pyridine triamine ( C4H8N6 ) 81 Benzoyl Choride 40 2-Amino-5-Methyl Pyridine 82 Benzyl Alcohol 41 2-Chloro pyridine 83 Benzyl dimethyl ammonium chloride 42 2-Cyano phenol 84 Boron Trichloride

12

RAW MATERIALS

SN NAME OF RAW MATERIAL SN NAME OF RAW MATERIAL 85 Bromine 135 ethyl chloroformate 86 BY1 136 Ethylene diamine 87 Camphene 137 Fenofibric acid 88 Catalyst ( resin ) 138 Floroboric Acid 89 catalyst nickel 139 Formaldehyde 90 Catalyst(Copper+) 140 Formamide 91 Catalyst(PTSA) 141 Glycidol 92 Caustic potash 142 Guaicol 93 Caustic soda 143 Guarcol 94 Cerium Chloride 144 HCl 95 CH3Ona 145 Heptaldehyde 96 Chlorine 146 Hexamethylene dicynide 97 Chloroacetyl chloride 147 Hexane 98 Chloroform 148 Hydrogen 99 Chlorosulfonic acid 149 hydrogen peroxide

100. Citric acid 150 Iodine 101 Clomiphene base 151 IPA 102 Cuprous cyanide 152 Iso propyl ether 103 cyanacetic acid 153 isobutyl aceto acetate 104 Cyanoacetamide 154 Isophthaldehyde 105 Cyanuric chloride 155 K2CO3 106 Cyclopentanone 156 KBH4 107 Cynamide 157 KOH 108 DCM 158 Liquid Ammonia 109 Dicyanamide 159 L-tartaric acid 110 Dicyclohexyl amine 160 Maleic anhydride 111 Diethanolamine 161 M-Aminophenol 112 diethyl ether 162 MCA 113 Diethylamine 163 M-Chloroaniline 114 Di-isopropyl ether 164 Methanol 115 Di-isopropyl ethylamine 165 methyl 2 bromo 3 -4-2-5 ethyl 2 pyridyl ethoxy phenyl

propiorate 116 dimethyl carbonyl chloride 166 methyl 2-2-4-4 chloro diphenyl methyl 1- piperazinyl

ethoxy acetate 117 Dimethyl malonate 167 methyl amine 118 Dimethyl sulfate 168 Methyl Chloro Formate 119 Dimethylamine 169 Methyl chloroacetate 120 dimethylamino ethyl chloride 170 Methyl magnesium chl 121 Dioxane ( solvent ) 171 Methyl-2-iodo Benzoate 122 DMF 172 MDC 123 DMI 173 m-hydroxyphenyl ethyl dimethylamine 124 DMSO 174 m-Nitrobenzaldehyde 125 EDC 175 monochloro acetic acid 126 EDTA 176 monochloro benzene 127 Ethanol 177 Monoethylene glycol(MEG) 128 Ether 178 monomethyl 1,1-cyclohexane diacetate 129 Ethyl 2,6 dichloro phenyl acetate 179 Morphene 130 Ethyl 4-4-4 hydroxydiphenyl methyl 1 piperidinyl 1

hydroxybutyl alfa alfa dimethyl benzene acetate 180 m-xylidine

131 Ethyl Acetate 181 N 4 hydroxy benzyl 3,4 dimethoxy benzamide 132 Ethyl aceto acetate 182 N chloro succinimide 133 Ethyl amine 183 N methyl N-Napthyl amine 134 Ethyl Chloro Acetate 184 N methyl piperazine

13

RAW MATERIALS SN NAME OF RAW MATERIAL SN NAME OF RAW MATERIAL 185 n- Pentanol 229 potassium bicarbonate 186 N-(5-amino-2-methyl phenyl)-4-)3-pyridinyl) -2-

pyridinamine (C16H15N2) 230

Potassium cyanide

187 N, N-Dimethyl-3-napthalenyloxy-3-(2-thienyl) propanamine

231Potassium salt of 3 cyano 5 methyl hexanoic acid

188 N,N dimethyl 3 4 methyl benzoyl bromo propanamide 232 Propyl Bromide 189 N,N dimethyl alfa 1 hydroxy cyclohexyl 4 methoxyphenyl

thioacetamide 233

Propylene glycol

190 N,N-bis ( acetyl ) 9H-Purine 2-6 diamine ( C9H10N6O2 ) 234 Propylene Oxide 191 Na2CO3 235 p-Toluene sulphonic acid(PTSA) 192 Na2S 236 PTSA 193 NaBH4 237 Pyridine 194 NaNH2 238 Raney Nickel ( Wet 10% ) 195 NaH 239 rBY1 196 NaoH 240 Soda Ash 197 n-Butyl lithium 241 Sodium acetate 198 NH4Cl 242 sodium azide 199 NH4OH 243 Sodium bicarbonate 200 n-Hexane 244 sodium borohydrate 201 Nickel 245 Sodium Carbonate 202 Nitric Acid (65%) 246 Sodium chloride 203 o- Phenylene Diamine 247 Sodium Cyanide 204 o-chloro benzoic acid 248 sodium ethoxide 205 Octyl phenol 249 Sodium iodide 206 O-methoxyphenol 250 Sodium metal 207 o-nitrobenzaldehyde 251 Sodium methoxide 208 o-xylene 252 Sodium Nitrate 209 P Formaldehyde 253 Sodium saccharin 210 Palladium on carbon 254 Styrene 211 Paraformaldehyde 255 Styrene oxide 212 P-Chlorobenzyl cyanide 256 H2SO4 213 PCl5 9 257 t-Butanol 214 pentyl chlorofumate 258 TEA 215 peracetic acid 259 Tetrafluoro boric acid 216 Petroleum Ether 260 THF (Tetra Hydrogen) 217 Phenol 261 Thio Urea 218 Phenyl acetaldehyde 262 Thiomer 219 Phenyl Ethyl Alcohol 263 Thionyl Chloride 220 Phosgene 264 Tiglic aldehyde 221 phosphoric acid 265 Toluene 222

Phosphoric acid(trimethyl ester) 266 Trans -4- 2 amino 3,5 dibromo benzylidene amino

cyclohexanol 223 Phosphorous oxychloride POCl3 267 tributyl tin azide 224 Phosphorous trichloride (PCl3) 268 Triethylamine 225 P-Hydroxy benzaldehyde 269 VinylMagnesium Br 226 Pinacolone 270 Xylene 227 Piperazine 271 Y-amino butyric acid 228 Pivalic Acid 272 Zinc Chloride

14

FINISHED PRODUCTS

SR. NO. NAME CAPACITY MT/YR

EXISTING PROPOSED

1. Advanced Intermediates 420 2550 1 s Methyl Phenyl Glycine Methyl Ester(sMPGM) 180 600 2 Methyl 5 Phenyl Imidazolidine 2,4-dione(rMPID) 240 900

1.1 Dichloro Phenyl Methyl Hydantoin 1050 1.2 Dibromo Phenyl Methyl Hydantoin 1.3 Dilodo Phenyl Methyl Hydantoin 1.4 Chloro Bromo Phenyl Methyl Hydantoin 1.5 DiChloro DiMethyl Hydantoin 1.6 Dilodo DiMethyl Hydantoin 1.7 Chloro Bromo DiMethyl Hydantoin 1.8 Bromo Hydantoin 1.9 Dimethyl Aminoacrylic Acid EthylEster

1.10 Methoxyacrylic acid methyl ester 1.11 Propionic Acid methyl ester 1.12 Methoxyacrylic acid ethyl ester 1.13 Glycide ethers 1.14 9-H-Carbazole-4-ol 1.15 2, 4-DiHydroxy-Benzonitrile 1.16 Isophthalonitrile 1.17 1-Cyano Acetate OR Propaenitrile, 2-(Acetyloxy) 1.18 Benzonitrile 1.19 Malononitrile 1.20 Propionitrile 1.21 2 Hydroxybenzonitrile 1.22 4 Hydroxybenzonitrile 1.23 Phthalodinitrile 1.24 Phthalonitrile 1.25 Lilial 1.26 6-Hydroxy Quinoline 1.27 6-Bromo Quinoline 1.28 6-Methoxy Quinoline 1.29 Methyl Isobutyl Ketone 1.30 4- Ethoxy -1,1,1- Trifluorobut-3-ene-2-one 1.31 4-Methoxy -3N-Amino Sulfonyl phenyl acetone 1.32 2-Allyl-4-Hydroxy-3-Methyl-2-Cyclopenten-1-One 1.33 2,4 DiChloro Velerophenone 1.34 4-Methoxy Acetophenone 1.35 Furan-2,5-Dicarboxylic Acid 1.36 2-Isopropyl-2-PhenylAcetic Acid 1.37 1,6-DiHydro-6-Oxo-Pyridazine-4-Carboxylic Acid 1.38 P- Nonylphenoxyacetic Acid 1.39 Cyano Acetic Acid 1.40 Tiglic Acid 1.41 Beta Benzoyl acetic acid

15

FINISHED PRODUCTS


EXISTING PROPOSED

1.42 4- Amino-2-Hydroxy -Benzoic Acid 1.43 2-Chloro-5-Methoxy Aniline HCI 1.44 Suberic Acid 1.45 Mesalazine (5 Amino Salicyclic Acid) 1.46 Chloro diMethoxy triazine 1.47 N-(4 Hydroxy Benzyl)3,4 dimethoxy benzamide 1.48 N,N-Bis (Chloroethyl) phenyl Sulphonamide 1.49 Dichlorobenzylidine 1.50 Imidazopyridine 1.51 Piperazine 1.52 2-Chloro-4,6-dimethoxy-1,3,5-triazine 1.53 4-Hydroxy -2-methyl 2H-1,2 Benzothiazine 1.54 Cyclopentanol 1.55 Chloroacetoxylidide 1.56 1-Bromo-1-tert-ButylBenzene 1.57 3-Phenoxy Benzaldehyde 1.58 2-Nitrolmino Imidazolidine 1.59 2-Amino-4-Chloro-6-Methoxy Pyrimidine 1.60 2-Amino-4,6-Dimethoxy Pyrimidine 1.61 2-Amino-4,6-Dihydroxy Pyrimidine 1.62 2-Amino-4,6-Dichloro Pyrimidine 1.63 Ethyl 3-(dimethylamino)acrylate 1.64 Chloromethyl Dimethyl Dioxalane 1.65 Ethyl Chrysanthemumate 1.66 (S)-tert-Leucino 1.67 DimethylFuran-2,5-Dicarboxylate 1.68 Ninhyrin Hydrate 1.69 1-Methyl Pyrazole 1.70 Ethyl Cyano Acetate 1.71 2,2-Dichloro -3,3-Dimethyl Butane 1.72 Tert-Butyl Acetylene 1.73 Ethyl3-dimethylaminoacrylate, beta -(beta-DAASE) 1.74 4 Chloromethyl2,2 dimethyl 1,3 dioxalane 1.75 Isophorene 1.76 Amino ethoxy Anisole 1.77 N-Pentyl Chloroformate 1.78 1-Cyanoethyl Acetate 1.79 Propargyl Chloride 1.80 1-Phenyl-3-Hydroxy-1-2,4-Triazole 1.81 1,8-Octanediol 1.82 1-Hydroxy Benzotriazole (HOBT) Hydrate

16

FINISHED PRODUCTS


EXISTING PROPOSED

2. Bulk Intermediates. Nil 6000

2.1 Meta Phenoxy Benzaldehyde 2.2 Di N Propyl Amine 2.3 Styrene Oxide 2.4 Acetonitrile 2.5 4 Cyanophenol 2.6 2 Cyanophenol

3. Perfumery & Cosmetics. Nil 450

3.1 Cyclo Pentanone 3.2 Cyclo Pentanol 3.3 Astroglide 3.4 Sandalica 3.5 Phenyl Ethyl Alcohol 3.3 Propiophenone 3.4 Methyl Propyl Ketone 3.5 Heptanone 3.6 Zinc Pyrithione 3.7 Styrallyl Acetate 3.8 Styrallyl Propionate 3.9 Benzethonium Chloride

3.10 Oxybenzone 3.11 Delta Deca Lactone 3.12 Ethyl Phenyl Glycidate 3.13 Phenyl Acetaldehyde Dimethyl Acetal 3.14 Phenyl Ethyl Acetate 3.15 Phenyl Ethyl Methyl Ether 3.16 Raspberry Ketone 3.17 Dihydroxy Methyl lasmonate 3.18 Phenyl Acetaldehyde

4. Pesticides. Nil 800

4.1 Azoxystrobin 4.2 Fenamidone 4.3 Carbendazim 4.4 Simazine 4.5 Napropramide

5. API’s. Nil 1200

5.1 Montelukast 5.2 Fexofenadine hydrochloride 5.3 Levocetirizine dihydrochloride 5.4 Cetirizine

17

FINISHED PRODUCTS


EXISTING PROPOSED

5.5 Chlorpheniramine 5.6 Fexofenadine 5.7 Hydroxyzine 5.8 Aripiprazole 5.9 Imatinib

5.10 Fludarabin 5.11 Itopride Hcl 5.12 Famotidine plus calcium 5.13 Omeprazol 5.14 Fenofibrate 5.15 Fenofibrate(Tricor) 5.16 Ezetimibe (Zetia) 5.17 Ambroxol 5.18 Metformin HCI 5.19 Nateglinide (Starlix) 5.20 Oxybutynin Chloride 5.21 Pioglitazone HCI 5.22 Amaryl- Glimepiride 5.23 Glimepiride 5.24 Glipizide 5.25 Divalprox Sodium 5.26 Gabapentin 5.27 Phenytoin 5.28 Pregabalin 5.29 Tamsulosin Hcl 5.30 Valporic Acid 5.31 Zonisamide 5.32 Zolpidem tartrate 5.33 Carbamazepine 5.34 Hydantoins 5.35 Bupranoll 5.36 Felodipine 5.37 Nisoldipine 5.38 Ranolazine 5.39 Lopressor (metroprolol tartrate) 5.40 Norvasc(amlodipine besylate) 5.41 Atenolol 5.42 Diltiazem 5.43 Nicardipine 5.44 Propanolol 5.45 Capecitabine 5.46 Irbesartan 5.47 Tamoxifen Citrate 5.48 Miradon

18

FINISHED PRODUCTS


EXISTING PROPOSED

5.49 Clopidogrel 5.50 Dabigatran 5.51 Sintrom 5.52 Ticlopidine 5.53 Warfarin 5.54 Buproprion 5.55 Citalopram 5.56 Duloxetine 5.57 Pramipexole 5.58 Venlafaxine 5.59 Moclobemide 5.60 Sertraline 5.61 Tofranil 5.62 Terbinafine Hcl 5.63 Fluconazole 5.64 Itraconazole 5.65 Miconazole (trade name Micatin or Daktarin) 5.66 Nifedipine 5.67 Epinephrine 5.68 Captopril 5.69 Nicardipine Hcl 5.70 Guafacine Hcl 5.71 Chlorothiazide 5.72 Guaifenesin 5.73 Ramipril 5.74 Nebivilol Hcl 5.75 Carvedilol 5.76 Guanfacine 5.77 Losartan/hctz 5.78 Metoprolol 5.79 Propranolol 5.80 Sidenafil 5.81 Telmisartan 5.82 Valacyclovir HCI’ Isonicotic Hydrazide 5.83 Ciprofloxacin 5.84 Clairthromycin 5.85 Azithromycin 5.86 Metronidazole 5.87 Nitrofurantoin Macrocrystals 5.88 Ketoconazole 5.89 Ephedrine (Rynatuss*) 5.90 Ibutilide (Corvert*) 5.91 Itraconazole (Sporanox*) 5.92 Ketoconazole (Nizoral*)

19

FINISHED PRODUCTS


EXISTING PROPOSED

5.93 Ketoprofen Mefenamic Acid 5.94 Piroxicam 5.95 Celecoxib 5.96 Diclofenac 5.97 Allytestrenol 5.98 Chlomiphene Citrate 5.99 Clopidogrel Hcl

5.100 Olanzapine 5.101 Eszopiclone 5.102 Aripiprazole 5.103 Quetiapine 5.104 Prochloroperazine 5.105 Tolterodine 5.106 Zidovudine 5.107 Donepezil Hcl 5.108 Ropinirole 5.109 Domperidone 5.110 Quatianine fumerate 5.111 Clomiphene Citrate 5.112 Epinephrine 5.113 Tamoxifen 5.114 Zoledronic acid 5.115 Alendronate sodium 5.115 Rivastigmine tartrate 5.116 Entacapone 5.117 Dexlansoprazole 5.118 Lidocaine

6. API Intermediate Nil 400

6.1 3-Cyano Quinoline 6.2 2-EthoxyBenzamide 6.3 4-Amino Salicyclic acid 6.4 2-Phenyl Butyric Acid 6.5 Mucic Acid 6.6 6- DiMethoxy-1-Indanone 6.7 7-Chloro Quinaldehyde 6.8 DiBenzo[b,f][1,4]Thiazepin-11(10H)-One 6.9 5-Chloro Indanone

6.10 Methyl-5-Chloro-1-Oxoindane-2-carboxylate 6.11 5-Chloro-2-Hydroxy-2-Methoxy Carbonyl Indanone 6.12 1-Indanone 6.13 2-Chloro-5-Nitrotoluene 6.14 Pyrazole 6.15 CycloOctanone

20

FINISHED PRODUCTS


EXISTING PROPOSED

6.16 Methyl 5-Acetyl Salicylate 6.17 N,N-Di-N-Propyl-2-methyl-3-nitro-phenyl ethyl amine 6.18 6-Methoxy-8-Nitroquinoline 6.19 Sodium Valporate

Indene-2-Carboxylic Acid-5-chloro-1-Hydrazinylidene-2,3-Dihydroxy-2-

6.20 Hydroxy Methyl Ester 6.21 3,5-Dinitro-4-Chlorobenzene Sulfonic Acid 6.22 3,4,5-Trimethoxy Toluene 6.23 1,2,4-Triazole Sodium 6.24 Vilsmeier Reagent 6.25 3,4-Dihydroxy-Benzaldehyde 6.26 Benzyl Chloroformate 6.27 S-methyl isothiourea hemisulphate 6.28 Pivaloyl Chloride

NOTE: Maximum 10 Nos. of products will be simultaneously produced at any given time in this Multi-purpose facility. The total production volume will not exceed 11400 MT/year. The total By-products will not exceed 2105 Mt./year.

LIST OF BY PRODUCTS

SR. NO. NAME CAPACITY 1. Sodium Sulfate. 1600 MT/year * 2. Potassium Bromide. 480 MT/year 3. Sodium Bromide. 25 MT/year

*(This is part of the existing product sMPGM)

HAZARDOUS SOLID WASTES.

TYPE OF WASTE CATEGORY NO. QUANTITY (TPY) FORM Residue and Wastes. 28.1 & 29.1 240 Semi Solid. Spent Organic Solvents. 20.2 60 Liquid. Chemical sludge from waste water treatment.

34.3 40 Solid.

Spent Catalyst. 35.2 5 Solid. Spent Carbon (from ETP). 35.3 270 Solid. MEE solids. 34.3 3000 Solid. Bio sludge. – 10 Solid. Discarded contaminated containers, barrels and bags/ liners.

33.3 12000 nos. 24000 nos.

Solid.

Filters and filter material which have organic liquids in them.

35.1 1 Solid.

21

SECTION 3

IDENTIFICATION OF

HAZARDS

22

BULK STORAGE AT TANK FARM.

PROPOSED

SR. NO. MATERIAL CATEGORY

QUANTITY (MT/

YEAR)

MAX. QTY. STORED (MT.)

NO. OF TANKS MOC SAFETY

FEATURES LOCATION

1. Acetone. Solvents requiring

Flameproof area.

191 8 1 MS Dyke. Explosive Tank Farm (150 m2).

2. Tetra Hydro Furan. 485 9 1 MS Dyke. 3. Toluene. 253 9 1 MS Dyke.

4. Acetic Acid. Acids. 1961 21 1 SS Dyke.

Tank Farm. (330 m2).

5. Hydrochloric Acid. Acids. 500 11 1 PP/FRP Dyke, scrubber.

6. Phenol. Others. 348 10 1 MS Dyke 7. Hydrogen Peroxide. Others. 1044 14 1 SS Dyke

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 1: TANK FARM. K-38, MIDC Butibori, Nagpur, Maharashtra.

23

NODE 1 : TANK FARM. SUB NODE 1.1: ACETIC ACID STORAGE TANK INSTALLATION. DESIGN INTENT : Acetic Acid SS storage tank 20 m3 capacity with dyke. Receipt, Storage and Handling Operations.

GUIDE WORD

PARAMETER DEVIATION CAUSE CONSEQUENCE PROTECTION MEASURES S P R RECOMMENDATIONS

None. Flow. No flow of Acetic Acid during road tanker unloading to storage tank or transfer to day tank from storage tank.

No material in the road tanker or storage tank. Valve failure/ blockage. Line blockage. Transfer Pump failure (loss of power, impeller came off or corroded etc.). Human error.

Delayed operation. Delayed operation. Spill hazard during blockage removal operation. Delayed operation. Delayed operation.

LG. Preventive maintenance. PPE. Training. Preventive maintenance. Supervision.

2

3

3

3

3

3

3

3

6

9

9

9

Log book record. SOP for blockage removal operation.

More. Flow. More flow of Acetic Acid during transfer to day tank from storage tank.

Valve malfunctioning. Human error.

Delayed operation. LI at storage tank. Improved supervision.

3 3 9 Preventive maintenance.

Less. Flow. Less flow of Acetic Acid during transfer to feed tank from storage tank.





24


GUIDE WORD


Reverse. Flow. Reverse flow. Dip pipe in the tank. Siphon in case of line failure.

Spill hazard. NRV in supply line. 3 2 6 Preventive maintenance.

As Well As.

Flow. As well as. Rust, dirt etc. Disturbed operation. Strainer in supply line. 2 3 6 Preventive maintenance.

Other Than.

Flow. Other than. Impurity / accidental mix up. Human error.

Depends on the mix up components.

Dedicated piping. Hence, not likely. Supervision. Process control check.

3 3 9

Other. Flow. Static discharge.

Static sensitive material Acetic Acid transfer by pump. Free fall of Acetic Acid in the vessel.

Static discharge as source of ignition in case of any spill and vapors coming in flammable range with air. Fire/ explosion hazard.

Supervision. Dip pipe provided in feed lines

5 4 20 Ground all containers during transfer or take precautionary measures against electrostatic loading.

Other. Flow. Release of liquid/ vapors.

Pump land leak. Gasket failure. Sampling. Vent release.

Spill Release of Acetic Acid vapors. Formation of flammable mixture with air. Fire/ Explosion hazard if finds source of ignition.

Open area. 4 3 12 Monitor the work place air born concentration of chemicals within prescribed limit. Provide leak detection system.

Other. Flow. Large spill. Failure of the vessel, tank etc. Due to impact/ mechanical failure.

Spill hazard. Dyke fire. If the flammable vapors finds source of ignition, fire hazard.

Supervision. Dyke. Fire fighting system.

5 3 15 Revise “On Site Emergency Plan” based on MCLS Study. Mock Drill to test the effectiveness of the plan.


25


GUIDE WORD


Other. Handling. Cleaning of the piping/ tank/ equipments.

Inspection, repair, maintenance work.

Residual vapors in the equipment/ piping fire hazard. Health hazard.

SOP. Supervision.

3 3 9 Work permit.

More. Temperature. More temperature at Acetic Acid storage tank.

Temperature indicator malfunctioning.

Release of vapors at vent of FB – 1209.

Supervision. 2 3 6 Regular calibration of instrumentation.

Less. Temperature. Less Temperature.

Winter season. Freezing likely. Failure of piping if material is trapped between the valves.

3 3 9

More. Pressure. More Pressure. More rate of pumping in and vent blockage. Vent blanked off. Plastic bag over vent. Vent choked. Flame trap choked. Vent connected to water seal. Vent too small. Vent modified. Flexible tubing connected to vent. In let of hot recycle liquid.

Pressurization. Vent inspection. 4 3 12 Preventive maintenance.


26


GUIDE WORD


Less. Pressure. Less Pressure. More rate of

pumping out and

vent blockage.

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

More Phase. Increase in

phases.

Moisture/ water in

feed rain.

Disturbed operation. Rain cap at vent.

As Well

As.

Composition Impurities. Contamination in

tanker.

Supply source.

Back flow in inert

gas supply.

Disturbed operation. Dedicated piping.

Process control checks.

NRV in inert gas supply

line.

3 2 6

More. Level. More Level. More feed in error,

excessive recycle

Acetic Acid feed.

Spill hazard. High level interlock in

feed line.

5 3 15 SOP.

Less. Level. Less Level. Less material in the

tank.

Starving of outlet pump

suction.

Low level interlock in

feed line.

3 3 9

Other. Handling. Emergency. Lightening. Tank fire. Lightening arrestor. 4 1 4


27

NODE 1 : TANK FARM. SUB NODE 1.2: ACETONE STORAGE TANK INSTALLATION. DESIGN INTENT : Acetone MS, under ground storage tank 20 m3 capacity. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No flow of Acetone during road tanker unloading to storage tank or transfer to day tank from storage tank.




2

3

3

3

3

3

3

3

6

9

9

9


More. Flow. More flow of Acetone during transfer to day tank from storage tank.




Less. Flow. Less flow of Acetone during transfer to feed tank from storage tank.







28


GUIDE WORD


As Well As.


Other Than.



Dedicated piping, hence, not likely. Supervision. Process ontrol check.

3 3 9


Static sensitive material Acetone transfer by pump. Free fall of Acetone in the vessel.


Supervision. Dip pipe provided in feed lines.




Spill Release of Acetone vapors. Formation of flammable mixture with air. Fire/ Explosion hazard if finds source of ignition.



Spill hazard. Fire. If the flammable vapors finds source of ignition, fire hazard.

Supervision. UG tank. Curb wall for containment. Fire fighting system.



Inspection, repair, maintenance work. External corrosion.


SOP. Supervision.

3 3 9 Work permit.


29


GUIDE WORD


More. Temperature. More temperature at Acetone storage tank.


Release of vapors at vent.



Winter season. Freezing not anticipated.

3 3 9 –

More. Pressure. More Pressure. More rate of pumping in and vent blockage. Vent blanked off. Plastic bag over vent. Vent choked. Flame arrestor choked. Vent connected to water seal. Vent too small. Vent modified. Flexible tubing connected to vent. In let of hot recycle liquid.



30


GUIDE WORD



pumping out and

vent blockage.


More. Phase. Increase in

phases.

Moisture/ water in

feed rain.

Disturbed operation/

quality issue.

Rain cap at vent. 2 2 4

As Well

As.

Composition. Impurities. Contamination in

tanker.

Supply source.

Back flow in inert

gas supply.




line.

3 2 6


excessive recycle

Acetone feed.


feed line.

5 3 15 SOP.


tank.


suction.


feed line.

3 3 9


31

NODE 1 : TANK FARM. SUB NODE 1.3: HYDROGEN PEROXIDE STORAGE TANK INSTALLATION. DESIGN INTENT : Hydrogen Peroxide SS storage tank 20 m3 capacity with dyke. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No flow of Hydrogen Peroxide during road tanker unloading to storage tank or transfer to day tank from storage tank.




2

3

3

3

3

3

3

3

6

9

9

9


More. Flow. More flow of Hydrogen Peroxide during transfer to day tank from storage tank.




Less. Flow. Less flow of Hydrogen Peroxide during transfer to feed tank from storage tank.





32


GUIDE WORD




As Well As.


Other Than.



Dedicated piping, hence, not likely. Supervision. Process control check.

3 3 9


Spill hazard.

Supervision. Dyke. Fire fighting system.

5 3 15 Do NOT use combustible materials to absorb or mop spills. Keep high volume low pressure water hose available the storage facility.



Residual vapors in the equipment/ piping.

SOP. Supervision.

3 3 9 Work permit.

More. Temperature. More temperature at Hydrogen Peroxide storage tank.

Decomposition. Pressurization. Supervision. 2 3 6 Consider alarm for temperature rise as indication of any decomposition.


Winter season. Freezing not anticipated.

– 3 3 9 –


33


GUIDE WORD


More. Pressure. More Pressure. More rate of pumping in and vent blockage. Vent blanked off. Plastic bag over vent. Vent choked. Flame trap choked. Vent connected to water seal. Vent too small. Vent modified. Flexible tubing connected to vent. Stabilizer depletion.

Pressurization. Vent inspection. 4 3 12 Establish testing and monitoring procedures of stabilizer (if any).

Less. Pressure. Less Pressure. More rate of pumping out and vent blockage.



34


GUIDE WORD


More. Phase. Increase in phases.

Foreign material/ water in feed rain.

Disturbed operation. Rain cap at vent. 2 2 4 Avoid recycle of contamination material to main storage tank even if small quantities. Provide closed arrangement for collection and disposal of left over material from hose after tanker unloading.

As Well As.

Composition. Impurities. Contamination in tanker. Supply source. Back flow in inert gas supply.

Disturbed operation. Dedicated piping. Process control checks. NRV in inert gas supply line.

3 2 6 Filters concentrate impurities and are a focal point for Hydrogen Peroxide decomposition. Use the largest mesh filter

element feasible. Make sure the filter is

equipped with a large-diameter pressure relief device.

Clean and/or replace the filter element frequently.

When the filter is not in service, rinse thoroughly with deionized water to eliminate stagnant Hydrogen Peroxide.

More. Level. More Level. More feed in error, excessive recycle Hydrogen Peroxide feed.

Spill hazard. High level interlock in feed line. Dyke.

5 3 15 Dyke drain valve keep closed, contain spill, flush with water, avoid any mix up in drain with organic.


35


GUIDE WORD



tank.


suction.


feed line.

3 3 9

Other. Handling. Piping. Passivation of

system before taking

in to use.

Decomposition. SOP for passivation. 3 3 9 Keep minimum number of valves,

avoid any Hydrogen Peroxide

trapped in the piping between

two valves if so provide relief

valve.

Avoid long piping runs.

Minimize valves and fittings.

Provide a pressure-relief

device in any line where

solutions containing

Hydrogen Peroxide can be

trapped.

Provide a physical break

between the process and

the bulk storage tank.


36

NODE 1 : TANK FARM. SUB NODE 1.4: HYDROCHLORIC ACID STORAGE TANK INSTALLATION. DESIGN INTENT : Hydrochloric Acid PP/ FRP storage tank 20 m3 capacity, with dyke & scrubber. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No Flow of material from road tanker to the Hydrochloric Acid storage tank.

No material in road tanker.

Pump failure. Isolation Valve failure. Power failure.

Delayed operation. SOP. PI at pump discharge line. Preventive M/T. Emergency power.

2

3

3

2

3

3

3

3

6

9

9

6

Provide SOP and check list of Safety measures during unloading Hydrochloric Acid from road tanker and during transfer operations.

Less. Flow. Less flow of material during road tanker unloading.

Transfer Hose failure in Hydrochloric Acid line.

Spill hazard. Quality hose. 3 3 9 Insist on quality hose and introduce regular inspection of hose.

More. Flow. More feed to plant.

Human error. Over flow, spill hazard. LI. Dyke, Acid proof flooring.

3 3 9 Improved supervision by trained personnel.

Other. Flow. Loss of containment.

Catastrophic failure of road tanker/ tank.

Spill hazard. Fire fighting system. Training. Dyke for containment of accidental spill.

4 4 16 “On Site Disaster Control Plan” based on MCLS study. Regular Inspection/ testing of the storage tanks. Keep adequate stock of neutralizing materials.


37

NODE 1 : TANK FARM. SUB NODE 1.4: HYDROCHLORIC ACID STORAGE TANK INSTALLATION. DESIGN INTENT : Hydrochloric Acid PP/ FRP storage tank 20 m3 capacity, with dyke & scrubber. Receipt, Storage and Handling Operations.

GUIDE WORD


Other. Flow. Leaks. Leak at pump seal, gasket etc.

Spill hazard. Health hazard. Corrosion.

Storage in open area. 5 4 20 Carry out work area monitoring for air born concentration of Hydrogen Chloride within prescribed limits under “The Second Schedule of Factories Act

More. Temperature.

More Temperature.

Accidental mix up. Refer compatibility study Annexure 1.

Vent to safe place.

3 3 9 SOP.

More. Pressure. More Pressure while transferring.

Valve failure or closed in error. Gasket failure.

Spill hazard. PI. 3 3 9 Provide splash guards over flange joints carrying acid under pressure to prevent splashing of acid leaking through joints due to gasket failures on workers working nearby.

Less. Pressure. Less Pressure. Vent blockage while pumping out.

Implosion. Spill hazard.

Supervision. 3 3 9 Regular inspection of vent.

More. Phase. Increase in number of phases.

No potential problems identified.

- - -

More. Level. Higher level at day tank.

Overfilling due to operator error.

Spill hazard. 1. LI. 2. Supervision.

3 3 9 Consider overflow line back to the storage tank of origin.


38

NODE 1 : TANK FARM. SUB NODE 1.5: PHENOL STORAGE TANK INSTALLATION. DESIGN INTENT : Phenol MS storage tank 20 m3 capacity with dyke. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No flow of Phenol during road tanker unloading to storage tank or transfer to day tank from storage tank.

No material in the road tanker or storage tank. Valve failure/ blockage. Line blockage. Transfer Pump failure (loss of power, impeller came off or corroded etc.). Less temperature.


LG. TI Preventive maintenance. PPE. Training. Preventive maintenance. Supervision.

2

3

3

3

3

3

3

3

6

9

9

9


More. Flow. More flow of Phenol during transfer to day tank from storage tank.




Less. Flow. Less flow of Phenol during transfer to feed tank from storage tank.







39


GUIDE WORD


As Well As.


Other Than.




3 3 9


Static sensitive material.


Supervision.




Spill Release of Phenol vapors. Formation of flammable mixture with air. Fire/ Explosion hazard if finds source of ignition.



Spill hazard. fire If the flammable vapors finds source of ignition, fire hazard.

Supervision. Dyke. Safety shower.



Inspection, repair, maintenance work. External corrosion.


SOP. Supervision.

3 3 9 Work permit.


40


GUIDE WORD


More. Temperature. More temperature at Phenol storage tank.

Excessive heating in error.


Supervision. 2 3 6


Winter season. Freezing. Heating and insulation to tank.

3 3 9 –

More. Pressure. More Pressure. More rate of pumping in and vent blockage. Vent blanked off. Plastic bag over vent. Vent choked. Flame arrestor choked. Vent connected to water seal. Vent too small. Vent modified. Flexible tubing connected to vent.



41


GUIDE WORD



pumping out and

vent blockage.


More Phase. Increase in

phases.

Moisture/ water in

feed rain.

Disturbed operation/

quality issue.

Rain cap at vent. 2 2 4

As Well

As.


tanker.

Supply source.




line.

3 2 6

More. Level. More Level. More feed in error, Spill hazard. High level interlock in

feed line.

5 3 15 SOP.


tank.


suction.


feed line.

3 3 9


42

NODE 1 : TANK FARM. SUB NODE 1.6: THF STORAGE TANK INSTALLATION. DESIGN INTENT : THF MS under ground storage tank 20 m3 capacity. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No flow of THF during road tanker unloading to storage tank or transfer to day tank from storage tank.

No material in the road tanker or storage tank. Valve failure/ blockage. Line blockage. Transfer pump failure (loss of power, impeller came off or corroded etc.). Human error.



2

3

3

3

3

3

3

3

6

9

9

9


More. Flow. More flow of THF during transfer to day tank from storage tank.




Less. Flow. Less flow of THF during transfer to feed tank from storage tank.







43


GUIDE WORD


As Well As.


Other Than.




3 3 9


Static sensitive material THF transfer by pump. Free fall of THF in the vessel.


Supervision. Dip pipe provided in feed lines.




Spill Release of THF vapors. Formation of flammable mixture with air. Fire/ Explosion hazard if finds source of ignition.









SOP. Supervision.

3 3 9 Work permit.


44


GUIDE WORD


More. Temperature. More temperature at THF storage tank.





Winter season. – – 3 3 9 –




45


GUIDE WORD



pumping out and

vent blockage.



phases.

Moisture/ water in

feed rain.

Disturbed operation. Rain cap at vent. 2 2 4

As Well

As.


tanker.

Supply source.

Back flow in inert

gas supply.




line.

3 2 6


excessive recycle

THF feed.


feed line.

5 3 15 SOP.


tank.


suction.


feed line.

3 3 9


46

NODE 1 : TANK FARM. SUB NODE 1.7: TOLUENE STORAGE TANK INSTALLATION. DESIGN INTENT : Toluene MS under ground storage tank 20 m3 capacity. Receipt, Storage and Handling Operations.

GUIDE WORD


None. Flow. No flow of Toluene during road tanker unloading to storage tank or transfer to day tank from storage tank.




2

3

3

3

3

3

3

3

6

9

9

9


More. Flow. More flow of Toluene during transfer to day tank from storage tank.




Less. Flow. Less flow of Toluene during transfer to feed tank from storage tank.







47


GUIDE WORD


As Well As.


Other Than.




3 3 9


Static sensitive material Toluene transfer by pump. Free fall of Toluene in the vessel.


Supervision. Dip pipe provided in feed lines




Spill Release of Toluene vapors. Formation of flammable mixture with air. Fire/ Explosion hazard if finds source of ignition.









SOP. Supervision.

3 3 9 Work permit.


48


GUIDE WORD


More. Temperature. More temperature at Toluene storage tank.





Winter season. – – 3 3 9 –




49


GUIDE WORD



pumping out and

vent blockage.



phases.

Moisture/ water in

feed rain.

Disturbed operation. Rain cap at vent. 2 2 4

As Well

As.


tanker.

Supply source.

Back flow in inert

gas supply.




line.

3 2 6


excessive recycle

Toluene feed.


feed line.

5 3 15 SOP.


tank.


suction.


feed line.

3 3 9

50

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

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

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

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

Br2, I2 or F2) or hydrohalogenation (with HCl, HBr or HF) to carbon-carbon double bonds.

FLOW CHART

Aromate

X2

ALX3

Aq or org solvent

→

→

→

→

HALOGENATIONS.

→

→

→

→

VOC.

HX.

X2.

↓

Precipitation.

↓

Filtration.

→

Mother liquor.

Aq. or Organic.

↓

Water → Product Washing. → Wash water.

↓

Solid Product.

Typical sequence of operations for Halogenation with precipitation of the products.

(Inputs on left and waste streams on right with colored background).

51

Product : Meta Phenoxy Benzaldehyde.

Chemical Name : M – Phenoxy Benzaldehyde.

CAS No. : 67 – 36 – 7.

Category : Bulk Intermediate.

STAGE I: PROCESS DESCRIPTION:

1. 4.6 Kg. of EDC, 1.66 Kg. of Catalyst & 1.0 Kg. of P-143 RM-01 are charged in a

flask.

2. Mass stirred at RT for 30 minutes & then cooled to 5oC, 0.782 Kg. of Bromine is

added. Chlorine gas is passed in reaction mass at 5oC to 9oC in 13-14 hrs.

3. Reaction mass is quenched in 9.0 Kg. of water 1.64 Kg. of cone. HCl. Stirred the

mass & layers separated. Organic layer is washed with 2 × 1.75 Lt. of water.

4. Organic layer is distilled atmospherically to remove EDC & then under vacuum to

get pure Stage-I product. Distilled Stage-1 weight: 1.2 Kg.

STAGE II: PROCESS DESCRIPTION:

1. Charged 1.2 Stage I product along with 0.65 Kg. Mono Ethylene Glycol & 3.86 gm.

Catalyst.

2. Mass heated to reflux temperature (130-132oC) & maintained for 1.5 hours.

3. Reaction mass cooled to 80oC to 90oC & applied low vacuum to remove excess

Mono Ethylene Glycol & water formed in reaction.

4. Later applied high vacuum to remove traces of Mono Ethylene Glycol. Product

remains in flask. Stage-II weight: 1.473 Kg.

STAGE III: PROCESS DESCRIPTION:

1. Added P-143 Stage II (1.47 Kg), Toluene (0.33 Kg), Phenol (O.682 Kg) & KOH

(0.45 Kg) to the reaction flask & heated to reflux (130oC).

2. Water formed was removed azeotropically. Added Catayst (6.0 gm) & heated the

reaction mass to 140oC to 145oC. Mainatined for 2-3 hours.

3. Mass cooled to RT & added 1.2 Kg water. Stirred for 15 minutes & separated

layers.

4. Organic layer washed with 1.0 Kg. of water. Organic layer is as such taken for next

stage. Stage-Ill organic layer weight: 1.96 Kg.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 2: HALOGENATION. K-38, MIDC Butibori, Nagpur, Maharashtra.

52

NODE 2 : HALOGENATION. SUB NODE 2.1: CHLORINE HANDLING. DESIGN INTENT : Receipt, Storage and Handling of Chlorine Tonners.

GUIDE WORD


Other. Flow. Release of Chlorine.

Impact during unloading of filled tonners from transport vehicle.

Release of Chlorine.

Dispersion in down wind direction having potential for off site serious consequences.

Health hazard.

EOT crane (min. capacity 2 mt.) is used for lifting and moving the filled tonner/ drum. Specially designed cradle with hook to ensure firm grip of tonner. Lifting equipment regular testing and maintenance as required statutorily to prevent failure. Training of the operatives in use lifting devices properly and following the procedure strictly. Outlet cap, gasket and protection bonnet in position for the tonner/ drum while handling.

4 3 12 Prepare written SOP for the Chlorine tonner drum handling. Maintain Chlorine leak control kit. Maintain SCBA. Maintain neutralization / scrubber in good working condition.


53


GUIDE WORD



Failure of lifting equipment due to exposure in corrosive atmosphere.

Release of Chlorine.

Dispersion in down wind direction having potential for off site serious consequences.

Health hazard.

EOT crane (min. capacity 2 mt.) is used for lifting and moving the filled tonner/ drum. Specially designed cradle with hook to ensure firm grip of tonner. Lifting equipment regular testing and maintenance as required statutorily to prevent failure. Training of the operatives in use lifting devices properly and following the procedure strictly. Outlet cap, gasket and protection bonnet in position for the tonner/ drum while handling.

4 3 12


54


GUIDE WORD



Movement of filled tonners to storage area.

Stored on ground floor, enclosed arrangement with easy emergency exit, protected from vehicular traffic and falling objects. Stored with outlet cap, gasket and protection bonnet in position. Stored horizontally, each tonner on roller supports. Chlorine leak detector.

4 3 12 Prepare written SOP for the Chlorine tonner/ drum handling. Maintain Chlorine leak control kit. Maintain SCBA. Maintain neutralization / scrubber in good working condition. Maintain Chlorine leak detector.


Movement of empty tonners / drum from storage area to transport vehicle.

Empty tonner/ drum may contain residual Chlorine. Release of Chlorine.

Stored on ground floor, enclosed arrangement with easy emergency exit, protected from vehicular traffic and falling objects. Stored with outlet cap, gasket and protection bonnet in position. Stored horizontally, each tonner on roller supports. Chlorine leak detector.

4 3 12 Prepare written SOP for the Chlorine tonner/ drum handling. Maintain Chlorine leak control kit. Maintain SCBA. Maintain neutralization/ scrubber in good working condition. Maintain Chlorine leak detector.


55


GUIDE WORD



External corrosion.

Storage shed chemically non - corrosive atmosphere. Complete protection against rainwater in storage room. Tonner room flooring sloped to ensure easy water drainage. Horizontal storage of tonner over rollers – one tier high only. Empties stored away from filled tonners. Chlorine leak detector. Ventilation ducting, blower, scrubber arrangement.



56


GUIDE WORD


More. Temperature. More temperature of Chlorine tonner during storage of filled tonners.

Exposure to heat, fire.

Temperature rise Pressurization Release of Chlorine.

Dispersion in down wind direction having potential for off site serious consequences

Health hazard.

Storage room away from any hot surfaces/ fired system, combustibles and areas where hot work like gas cutting welding is carried out. Work permit system. Portable fire extinguishers. Fire hydrants. Chlorine leak detector.


More. Temperature. More temperature of Chlorine tonner during storage of filled tonners.

Summer season.

Temperature rise Pressurization Release of Chlorine.

Dispersion in down wind direction having potential for off site serious consequences

Health hazard.

Chlorine tonners are protected from sun in covered drum room.



57


GUIDE WORD


More. Pressure. More pressure of Chlorine tonner during storage of filled tonners.

Exposure to heat, fire.

Pressure rise pressurization gasket failure. Release of Chlorine. Chlorine tonners are filled with liquid Chlorine up to 80 %. Volumetric expansion of gas will cause the bursting of the tonner if CHLORINE TONNER heated BEYOND 70oC.

Storage room away from any hot surfaces/ fired system, combustibles and areas where hot work like gas cutting welding is carried out. Work permit system. Portable fire extinguishers. Fire hydrants. Chlorine leak detector.


More. Pressure. More pressure of Chlorine tonner during storage of filled tonners.

Summer season.

Pressure rise pressurization gasket failure. Release of Chlorine. Dispersion in down wind direction having potential for off site serious consequences.

Health hazard.

Chlorine tonners are protected from sun in covered drum room.



58


GUIDE WORD


As Well As.

Phase. Released liquid evaporating to gas phase.

Accidential liquid release.

Liquid Chlorine evaporating to gas phase volume increase by factor of 460 there by making control difficult.

The tonners are stored on rollers such that the valve position can be changed by rotating through 180 degree to convert liquid release to gas release. Training. Chlorine leak detector. Chlorine leak control kit.

4 3 12

Less. Level. Less/ no height of drum storage level from ground level.

Storage on ground.

Difficulty in operation of Chlorine leak control kit in certain release scenerios requiring inserting chain bellow the drum.

The tonners are stored on rollers at adequate height from ground level for ease of operation of Chlorine leak control kit. Training. Chlorine leak detector. Chlorine leak control kit.

4 3 12


59

NODE 2 : HALOGENATION. SUB NODE 2.2: BROMINE HANDLING. DESIGN INTENT : Receipt, Storage and Handling of Bromine.

GUIDE WORD


Other. Handling. Bromine storage of bottles.

Bottles crates handling manually.

Spill in uncontrolled manner, health hazard.

Supervision. 3 3 9 Store Bromine in a dry, well-ventilated area, protected from moisture and excessive heat or cold.




Supervision. 3 3 9 Bromine bottles should be transported in rubber bottle carriers or a closed container that is sufficiently padded to avoid bottle breakage.




Supervision. 3 3 9 Provide pit, filled with sand at Bromine storage area.



Spill, health hazard. Supervision. 3 3 9 Keep stock of neutralizing materials such as Sodium Thio Sulphate stock Sodium Meta Bi Sulphate, Potassium Carbonate, Sodium Carbonate or Sodium Bicarbonate.

As Well As.

Solid waste. Disposal of solid waste generated during spill handling.

Neutralization dry Bromates (products of Sodium Hydroxide neutralization of Bromine). Sand soaked with spill/ waste generated during spill control.

Environmental issues. Hazardous solid waste disposal to CHWTSDF.

3 3 9 Neutralization dry Bromates (products of Sodium Hydroxide neutralization of Bromine) are powerful oxidants and are shock sensitive. They must be handled with extreme care. Prepare SOP for disposal of sand soaked with spill/ waste generated during spill control.


60

NODE 2 : HALOGENATION. SUB NODE 2.2: BROMINE HANDLING. DESIGN INTENT : Receipt, Storage and Handling of Bromine.

GUIDE WORD


Other. Handling. Bromine

storage of

bottles.

Bottles crates

handling manually.

Spill, health hazard. Supervision. 3 3 9 Provide scrubber connection to

Bromine storage cabinet or

provide dedicated scrubber.

Other. Handling. Bromine spill

handling.

Broken bottle of

Bromine

Health hazard. Supervision. 3 3 9 Provide leak detectors at the

vent of scrubber to ensure the

performance of the scrubber or

consider suitable interlocks.

Other. Handling. Bromine spill

handling.

Sand soaked with

Bromine.

Health hazard. Supervision. 3 3 9 Prepare SOP for disposal of

sand soaked with spill/ waste

generated during spill control.

Other. Handling. Bromine

handling.

Human error in

handling.

Health hazard. Supervision. 3 3 9 Provide training to concerned

employees in Bromine handling.


61

NODE 2 : HALOGENATION. SUB NODE 2.3: PROCESS OPERATIONS. DESIGN INTENT : Product: Meta Phenoxy Benzaldehyde – Stage I.

GUIDE WORD


None Flow of Chlorine to chlorinator.

No flow of Chlorine to chlorinator.

Chlorine tonner empty. Dip pipe blockage. Line blockage.

Delayed operation Number of Chlorine tonners are connected to header. Rotameter in the Chlorine line. Supervision. PI at Chlorine feed header.

2 3 6

More. Flow. More flow at vent.

Uncontrolled/ more addition of Chlorine. Quenching operation, washing.

More flow at vent. SOP. Reflux Condenser Supervision.

4 3 12

Less. Flow. Less flow of water to jacket of the reactor.

Cooling water system malfunctioning.

Temperature rise due to reaction exotherm.

Supervision. TI on reactors.

4 3 12 Provide PI in cooling water line.

Reverse. Flow. Reverse flow. Back flow reverse flow at chlorine line. Common vent.

Disturbed operation. Barometric leg. NRV. Supervision.

3 3 9

Reverse. Flow. Reverse flow of reaction mass to Chlorine tonner.

Negative pressure at Chlorine tonner on becoming empty.

Damage to Chlorine tonner / pressurization is likely.

Barometric leg in Chlorine header provided.

4 2 8

Reverse. Flow. Reverse flow of scrubber solution to chlorinator.

Flooding at scrubber.

Disturbed operation. Trap/ separator provided.

3 3 9

More. Temperature. More temperature.

Reaction exotherm. Emission at vent. Process control. Supervision.

3 3 9


62


GUIDE WORD


Less. Temperature. Less temperature.

Loss of heating medium.

Low temperature process requirement.

Stand by cooling arrangement.

3 3 9

More. Pressure. More Pressure. Reaction exotherm Excessive heating. More rate of Chlorine / liquid Chlorine feed in error.

Pressurization, gasket leak. Explosion hazard. Loss of containment.

Process control. Supervision. SRV. RD.

5 4 20 DMP. Mock Drill. Fire Drill. Training.

Less. Pressure. Less Pressure. Fast pumping out/ fast cooling when vent closed.

Vacuum in the system. Implosion hazard.

Equipments are designed for vacuum. System vented to atmosphere.

5 2 10

More. Phase. More phases. Loss of turbulence / agitation.

Not significant. 3 3 9


Wrong connection of Chlorine tonner valve.

Liquid Chlorine entering the piping/ system. Pressure development.

Training. 4 3 12 SOP.

As Well As.

Composition. Impurities. Side reaction products. By products.

Poorly biodegradable and toxic, environmental issues.

Process control. Scrubber. Supervision.

3 3 9 Obtain MSDS of impurities, intermediates, side reaction products and decomposition products, (if any).

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

Entrainment, ingress of material in vent line.

Sight glass/ glass equipment

3 3 9 Provide trap in vent line.

Less. Level. Less level. Less batch charging in error.

Thermowell may not dip. Unsafe condition.

SOP. Supervision.

3 3 9


63


GUIDE WORD


Other. Handling. Solvent EDC handling.

Minor spill, receiver vents, sampling operation. Gland leaks Exposure to solvent vapors.


Fume hoods provision. 4 5 20 Carry out work area monitoring for maintaining air born concentration of chemicals within prescribed limit as prescribed in “The Second Schedule of Factory Act 1948”.

Other. MOC. Corrosion. Corrosive acidic materials.

Leaks. MOC Glass/ MSGL. 4 3 12

Other. Handling. Effluent generation.

Quenching operation.

Effluent generation only chlorinated hydrocarbons with a low degree of chlorination are degradable in biological waste water treatment plants.

ETP, The biological degradability of halogenated hydrocarbons (especially aromatics) decreases as their halogen content increases.

3 3 9

Other. Handling. Solid waste disposal.

Spent catalyst. Spill / waste generated during Bromine spill control.

No solid waste of catalyst. Dry Bromates (products of Caustic neutralization of Bromine) are powerful oxidants and shock sensitive.

Supervision. SOP.

3 3 9

Other. Storage. Accidental mix up of chemicals at ware house.

Large number of chemicals storage at ware house.

Reactivity / compatibility hazards due to large number of chemicals.

5 4 20 Rationalize the storage and handling of chemicals considering compatibility and reactivity hazards.


64


GUIDE WORD


Other. Storage. Accidental large spill of solvent.

Loss of containment. Spill hazard. Health hazard. Fire/ explosion hazard.

Flameproof electrical. 5 3 12 DMP. Fire hydrant system.

Other. Composition. Impurities. Contamination in feed. Supply source Same equipments are used for more than one operation/ product stage hence, increases the probability of deviations in operation/ human error especially of unintentional mix up/ contamination hence introduce product change over SOP.

The presence of contaminants can cause over pressurization in the reactor due to undesirable reactions. Disturbed operation.

Process control checks. 4 3 12 Obtain MSDS for the impurities (hazardous chemicals, if any) also for study decomposition products, reaction products etc. Provide dedicated piping, avoid hoses.

Other. Handling. Vessel entry. Inspection / maintenance.

Toxic gases in the reactor/ tank. Health hazard. Fire hazard.

Supervision. Work permit for hot work and vessel entry operation.

3 3 9


65


GUIDE WORD


Other. Handling. Release of Chlorine.

Continuous release of Chlorine caused by copper tube failure.

Toxic gas release, health hazard. May result in off site consequences. Chlorine gas is two and half times heavier than air and settles on ground level. It does not diffuse quickly into the atmosphere so its toxic effect in the air will be felt longer period.

Chlorine leak control kit. Mobile FRP hood. Scrubber.

4 3 12 Training to operatives in Chlorine leak control kit and SCBA handling. Insist on spiral in copper tube to avoid stresses during handling. Use proper gaskets.

Other. Handling. Release of Chlorine.

Continuous release of Chlorine caused by a break/ breach in the pipeline.

Toxic gas release, health hazard. May result in off site consequences.

Chlorine leak control kit. Mobile FRP hood. Scrubber.

4 3 12 Training to operatives in chlorine leak control kit and SCBA handling. Insist on spiral in copper tube to avoid stresses during handling. Use proper gaskets. Preventive maintenance of piping.


66

NODE 2 : HALOGENATION. SUB NODE 2.4: VENT SCRUBBER. DESIGN INTENT : Vent Gas Scrubber.

GUIDE WORD


None. Flow. No circulation of Caustic solution at absorption tower.

Transfer Pump failure (power failure, impeller came off, coupling failure etc.

Release of Chlorine at vent.

Supervision. PI at pump discharge line. Emergency power supply (DG Set). Stand by pump.

3 3 9 Provide leak detectors at the vent of scrubber to ensure the performance of the scrubber or consider suitable interlocks.


Valve failure. Release of Chlorine at vent.

Supervision. 3 3 9 Preventive maintenance.


Line blockage. Spill hazard during blockage removal operation.

Supervision. Safety shower and eye wash fountain. PPE.

3 3 9 SOP for blockage removal operation.

Less. Flow. Leakages in line pump.

Spill hazard. Health hazard.

Supervision. 3 3 9 Keep minimum flange joints. Consider plant layout to contain and route the spill and floor washings to safe place for disposal.

Less. Flow. Gland leakage. Spill hazard. Health hazard.

Supervision. 3 3 9 Keep minimum flange joints. Consider plant layout to contain and route the spill and floor washings to safe place for disposal.

Less. Flow. Less flow at scrubber.

Blower not working (power failure, impeller came off, coupling failure etc.

Accumulation of Chlorine in drum room.

Interlock of Chlorine leak detectors with blowers.

3 3 9 Carry out work area monitoring for Chlorine concentration within the prescribed limit in Schedule II Of “The Factory Act, 1948” Section 41 F.


67


GUIDE WORD


Less. Flow. Less Caustic solution circulation to scrubber.

Circulation pump malfunctioning.

Release of Chlorine at vent.

Supervision. Process control checks.

4 3 12 Consider need to provide Chlorine leak detector at the vent of the caustic scrubber.

Reverse flow.

Flow. Reverse flow of circulating Caustic solution at re-circulation pumps.

Loss of power. Disturbed operation. NRV in discharge line. 3 3 9

Reverse flow.

Flow. Reverse flow of scrubber solution to chlorinator.

Flooding at scrubber.

Disturbed operation. Absorption tower is located on the Caustic solution tank hence flooding of the Absorption tower not likely.

5 5 10

Other. Handling. Vessel entry. Inspection / maintenance.

Toxic gases in the reactor/ tank. Health hazard. Fire hazard.

Supervision. 2 4 8 Introduce work permit for hot work and vessel entry operation.

Other. Flow. Large spill of Caustic soda solution.

Catastrophic failure of at Caustic solution PP/ FRP tank at the scrubber.

Spill hazard. Safety shower and eye wash fountain. Adequate PPE.

3 3 9 Regular inspection, testing of PP/ FRP storage tanks. Maintain adequate stock of neutralizing materials. Provide adequate containment of accidental spill arrangement.


68


GUIDE WORD


More. Temperature. More temperature at Caustic solution at the scrubber tank.

Heat of neutralization.

Disturbed operation. TI at Caustic solution circulation line at the scrubber tank.

3 3 9 Regular Calibration of TI.

Less. Temperature. Less temperature at Caustic solution at the scrubber tank.

Winter season. Freezing not likely. 4 2 8

More. Pressure. More pressure at scrubber.

Vent blockage. Pressurization at scrubber system. Leakage at PP/ FRP ducting.

Supervision. 3 3 9 Regular inspection of vent.

More. Pressure. More pressure. More rate of in case of valve failure.

Pressurization at scrubber system.

Vent. System designed for anticipated flow rates. Supervision. Preventive maintenance.

3 3 9


More charging of Caustic flakes.

Blockage of the suction nozzle of circulation pump. Malfunctioning of Scrubber. Release of Chlorine gas at vent.

Caustic flakes are charged through nozzle in dissolving basket.

3 3 9 SOP.


69


GUIDE WORD


Less. Composition. Less concentration of the Caustic solution at the scrubber tank.

Depletion of the Caustic in the circulating solution.

Malfunctioning of the scrubber. Release of Chlorine gas at the vent.

Process control checks. Supervision.

3 3 9 Provide dedicated piping, avoid hoses.


Caustic flakes are used for make up.

Malfunctioning of the scrubber. Release of Chlorine gas at the vent.




Human error. Malfunctioning of the scrubber. Release of Chlorine gas at the vent.



Other than.

Composition. Impurities. From supply source of Caustic solution.

Disturbed operation. Process control checks. Supervision.

3 2 6 SOP.

Other than.

Composition. Wrong material. Mix up in error or wrong feed e.g. Alum solution.

Disturbed operation. Process control checks. Supervision.

3 2 6 SOP.

More. Level. More level at Caustic solution tank of the scrubber.

Human error during charging of Caustic solution.

Overflow at caustic solution tank of the scrubber. Spill hazard.

Level gauge at caustic solution tank. Corrosion resistant flooring around the caustic solution tank.

4 3 12


70


GUIDE WORD


Less. Level. Less level at

Caustic solution

tank of the

scrubber.

Human error. Malfunctioning of the

scrubber.

Release of Chlorine gas

at the vent.

Supervision. 4 3 12 Regular inspection.

Provide leak detector at the vent

of the scrubber.

Less. Level. Less level at

Caustic solution

tank of the

scrubber.

Human error. Malfunctioning of the

scrubber.

Release of Chlorine gas

at the vent.

Supervision. 4 3 12 Regular inspection.

Provide leak detector at the vent

of the scrubber.

71

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

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

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

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

FLOW CHART

Hydrogen

Organic

Catalyst

→

→

→ HYDROGENATION.

→

→

→

VOC.

Hydrogen.

unreacted.

↓

Filtration. → Spent catalyst.

↓

Purification. → Residue.

↓

Product.

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

Product : Delta Deca Lactone.Chemical Name : 705 – 86 – 2.CAS No. : Category : Perfumery & Cosmetics. Process Description

1. Cyclopentanone and Heptaldehyde are condensed, reacted with Oxalic acid, heated in Toulene till all water is removed.

2. Cooled solvent toluene rec, reaction product is Hydrogenated in Methanol for 4-5 hours.

3. The product obtained is taken up in EDC and oxidised with 40% Peacetic Acid at low temperature.

4. Check TLC. When 0oC separate layers. 5. Organic layer is washed free of peroxides. 6. Distill EDC and then crude is distilled under vaccum.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 3: HYDROGENATION. K-38, MIDC Butibori, Nagpur, Maharashtra.

72

NODE 3 : HYDROGENATION. PRODUCT: DELTA DECA LACTONE. DESIGN INTENT : Hydrogenation process using Hydrogen. Process step 2.

GUIDE WORD

PARAMETER DEVIATION CAUSE CONSEQUENCE PROTECTION MEASURES

S P R Action

None. Flow. No flow of cooling water.

No flow of cooling water to Hydrogenation reactor.

Uncontrolled reaction. Pressurization.

SOP. Supervision.

5 3 15

More. Flow. More flow. More flow of Hydrogen.

Release of unreacted Hydrogen at vent/ pressurization.

Vent. 5 3 15 Provide flame arrestor in vent of Hydrogen vents and locate flame arrestors at to convenient place for ease of maintenance.

Less. Flow. Less flow. Less flow of cooling medium to condenser.

Emission at condenser vent.

SOP. Reflux condenser. Supervision.

4 3 12

Reverse Flow. Reverse flow.

Reverse flow at Hydrogen feed line.

Dip pipe in the reactor, feed line fracture, siphon.

NRV in Hydrogen feed line.

4 3 12

Other. Flow. Static charge.

Handling of static sensitive materialsHydrogen and Methanol.

Static charge as source of ignition, fire/ explosion hazard.

Equipments are earthed. Flameproof electrical confirming to Class IIC.

5 4 20 Provide effective measures for prevention of accumulation of static charge to a dangerous extent.


73


GUIDE WORD


S P R Action


More rate of addition of Hydrogen.

Temperature rise as Hydrogenation is an exothermic reaction.

Hydrogenation is a mild exothermic reaction and the equilibrium usually lies far towards the Hydrogenated product under most operating temperatures.

3 3 9


Loss of heating medium.

Disturbed operation. Supervision. 2 2 4

More. Pressure. More Pressure.

Reaction exotherm. Excessive heating.

Pressurization, gasket leak. Explosion hazard.

Process control.

Supervision.

SRV.

RD.

5 4 20 DMP.

Mock Drill.

FIRE Drill.

Training.

Less. Pressure. Less Pressure.

Fast pumping out/ fast cooling when vent closed.


Equipments are designed for vacuum.

2 2 4

More. Phase. More phases.

Gas – liquid separation.

Delayed operation 2 2 4

As Well As.

Composition. Impurities. Side reaction products.

Quality issues. Hydrogenation reactions generate little or no unwanted by-products.

3 3 9


74


GUIDE WORD


S P R Action

As Well

As.

Composition. Other than

desired

material.

Oxygen in Nitrogen

cylinder in error.

Fire / explosion

hazard.

Supervision. 5 3 15 Check the purity of Nitrogen

cylinder (for Oxygen) in case

Nitrogen cylinder is used for

inerting.

More. Level. More level. Human error.

Excessive charging

of batch.

Entrainment, ingress

of material in vent

line.

Sight glass/ glass

equipment.


Less. Level. Less level. Less batch

charging in error.

Thermowell may not

dip. Unsafe

condition.

SOP.

Supervision.

3 3 9

Other. Handling. Solvent

handling.

Minor spill,

receiver vents,

sampling operation

Gland leaks

Exposure to

solvent vapors.

Health hazard due to

vapors emissions at

work place.

Fume hoods

provision.

4 5 20 Carry out work area monitoring for

maintaining air born concentration

of chemicals within prescribed

limit as prescribed in “The Second

Schedule of Factory Act 1948”.


75


GUIDE WORD


S P R Action

Other. Handling. Effluent

generation.

Waste water

streams from

process.

Environmental

issues.

ETP provided. 3 3 9

Other. Handling. Solid waste

disposal.

Spent

Hydrogenation

catalyst.

Pd/C.

Environmental

issues.

The spent

catalysts are

treated as wastes/

reclaimed for

recycle.

Hazardous solid

waste disposal to

CHWTSDF.

3 3 9

Other. Storage. Leak at

Hydrogen

cylinder.

Abuse in handling

of Hydrogen

cylinder handling.

Fire / explosion

hazard.

Supervision.

Shed.

5 4 20 DMP.

Leak detector.

Water sprinkler.

76

The term oxidation includes many different processes, but in general it describes the

addition of one or more Oxygen atoms to a compound. Atmospheric Oxygen is by far the

most important, and the cheapest, oxidising agent although the inert Nitrogen

component will dilute products and generate waste gas streams. Other oxidising agents

include Nitric Acid, Sulphuric Acid, Oleum, Hydrogen Peroxide, Organic Peroxides and

Pure Oxygen. In general terms, organic materials can be oxidised either by heterolytic or

homolytic reactions, or by catalytic reactions (where the oxidising agent is reduced and

then re-oxidised). Oxidation generally means the addition of an electron-donating atom

(such as Oxygen) and/or the removal of Hydrogen to a compound.

FLOW CHART

Oxidizing agent

Organic

Catalyst

→

→

→

OXIDATION.

→

VOC.

↓

Filtration. → Spent Catalyst.

↓

Purification. → Residue.

↓

Product.

Typical sequence of operations for Oxidation.

(Inputs on left and waste streams on right with colored background).

77

Product : Delta Deca Lactone.Chemical Name : 705 – 86 – 2.CAS No. : Category : Perfumery & Cosmetics.

Process Description:

1. Cyclopentanone and heptaldehyde are condensed, reacted with oxalic acid, heated in

toulene till all water is removed.

2. Cooled solvent toluene rec, reaction product is hydrogenated in methanol for 4-5

hours.

3. The product obtained is taken up in EDC and oxidised with 40% peacetic acid at low

temperature.

4. Check TLC, When 0oC separate layers.

5. Organic layer is washed free of peroxides.

6. Distill EDC and then crude is distilled under vaccum.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 4: OXIDATION. K-38, MIDC Butibori, Nagpur, Maharashtra.

78

NODE 4 : OXIDATION. PRODUCT: DELTA DECA LACTONE. DESIGN INTENT : PROCESS STEP NO 3.

GUIDE WORD


S P R RECOMMENDATIONS

None. Flow. No flow of cooling water to oxidation reactor.

Power failure. Cooling water failure.

Uncontrolled reaction. Pressurization / explosion hazard.

SOP. Supervision.

5 3 15


More flow of oxidising agent.

Uncontrolled reaction. Pressurization / explosion hazard.

SOP. Supervision.

5 3 15



SOP. Reflux condenser. Supervision.

4 3 12

Reverse.

Flow. Reverse flow at vent system.

Reverse flow at vent system as common vent.

Disturbed operation. SOP. Supervision.

3 3 9

Other. Flow. Static charge.

Static sensitive solvents.


Equipments are earthed.



Reaction exotherm. Emission at vent. Process control. Supervision.

4 3 12


Excessive cooling. Freezing not anticipated.

Compatible cooling medium.

2 2 4


79


GUIDE WORD




Faster addition of controlled reactant. Accumulation of reactant on loss of turbulence. Reaction exotherm – moderate. Accidental mix up.




Less. Pressure. Less Pressure.

Fast pumping out/ fast cooling when vent closed.



2 2 4

More. Phase. More phases.

Not anticipated. Not significant. 2 1 2

As Well As.

Composition. Impurities. Partial oxidation, Oxidation reactions may produce tars and ashes.

Disturbed operation. Process control. Supervision.

3 3 9



Sight glass/ glass equipment.




SOP. Supervision.

3 3 9


80


GUIDE WORD



Other. Handling. Emissions. Minor spill, receiver vents, sampling operation. Gland leaks Exposure to solvent vapors.


Ventilation system. 4 5 20 Carry out work area monitoring for maintaining air born concentration of chemicals within prescribed limit as prescribed in “The Second Schedule of Factory Act 1948”.

Other. Handling. Effluent generation.

Waste water streams from process.

Environmental issues.

ETP provided. 3 3 9

Other. Handling. Solid waste disposal.

Solid waste not anticipated

Insignificant. 3 2 6

Other. Handling. Peacetic acid handling.

Peacetic Acid/ Acetyl Hydroperoxide accidental spill.

May explosively decompose on shock, friction, or concussion. May explode on heating. The substance is a strong oxidant and reacts violently with combustible and reducing materials.

SCBA Stabilized.

4 3 12 Provision to contain effluent from fire extinguishing. Separated from combustible, reducing substances and incompatible materials. Rinse contaminated clothes (fire hazard) with plenty of water.

Other. Storage. Accidental large spill of solvent.

Loss of containment.

Spill hazard. Health hazard. Fire /explosion hazard.

Flameproof electrical.

5 4 20 DMP. Fire hydrant system.

81

Hydrolysis involves the addition or substitution of water (H2O) into a compound.

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

substances. Hydration is the process variant where water reacts with a compound

without causing its decomposition.

Environmental issues of Hydrolysis processes;

Air: There are generally low VOC arisings from reactors.

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

Product : 1, 8 – Octanediol.Chemical Name : 1, 8 – Octanediol.CAS No. : 629-41-4.Category : Advanced Intermediate.

Process Description:

1. Hexamethylene Dicynide was reacted with Methanol.

2. After Hydrolysys with H2SO4 to give 1, 8 – Octanoic Acid.

3. Methyl Ester is reduced by Sodium Boro Hydride in Methanol to give a 1, 8 –

Octanediol.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 5: HYDROLYSIS. K-38, MIDC Butibori, Nagpur, Maharashtra.

82

NODE 5 : HYDROLYSIS. EQUIPMENT: REACTOR. DESIGN INTENT :

GUIDE WORD


None. Flow. No addition of Sulfuric Acid to reactor.

Valve failure. Delayed operation. Preventive

maintenance.

2 2 4

More. Flow. More rate of

addition of

Sulfuric Acid.

Uncontrolled

process

opareation.

Vapors at vent. SOP.

Reflux condenser.

Supervision.

4 3 12

Less. Flow. Less flow. Less flow of

cooling medium to

condenser.

Emission at

condenser vent.

SOP.

Reflux condenser.

Supervision.

4 3 12

Reverse

.

Flow. Reverse flow. Not anticipated. – – –

Other. Flow. Static charge. Static sensitive

solvent Methanol.


Equipments are

earthed.


More. Temperature. More

temperature.

Reaction exotherm

– mild.

Emission at vent. Reflux condenser

provided.

3 3 9

Less. Temperature. Less

temperature.

Excessive cooling. Not significant. Freezing not anticipated.

Supervision. 2 2 4


83


GUIDE WORD



Reaction exotherm (mild).




Less. Pressure. Less Pressure. Fast pumping out/ fast cooling when vent closed.



5 2 10

More. Phase. More phases. Vapors. Not significant. 2 2 4

As Well As.

Composition. Impurities. Side reactions products. Hydrolysis involves the reaction of an organic with water to form two or more new substances.

Not significant. Process control. Supervision.

3 3 9




3 3 9 Provide vacuum trap in vacuum line.



SOP. Supervision.

3 3 9


84


GUIDE WORD


Other. Handling. Solvent

handling.

Minor spill,

receiver vents,

sampling

operation.

Gland leaks

Exposure to

solvent vapors.

Health hazard due to

Methanol vapors

emissions at work

place.

Ventilation hood. 4 5 20 Carry out work area

monitoring for maintaining air

born concentration of

chemicals within prescribed

limit as prescribed in “The

Second Schedule of Factory

Act 1948”.

Other. Handling. Effluent

generation.

Mother liquor.

Washings.

Environmental issues. ETP provided. 3 3 9

Other. Handling. Solid waste

disposal.

Spill handling. Not significant. Hazardous solid

waste disposal to

CHWTSDF.

3 3 9

Other. Handling. Corrosive

chemicals

handling.

Handling of

Sulfuric Acid.

Health hazard. 3 3 9 Provide safety shower and eye

wash fountain near corrosive

chemicals handling area.

85

Solvents are recovered by distillation and recycled for the same product.

FLOW CHART

Feed solvent. → DISTILLATION →

VOC

Residue.

↓

Solvent for reuse.

The distillation activity is carried out for minimizing the raw material cost & use of fresh

solvent in the process. As per the Policy to ‘recycle & reuse’ for Environmental aspect.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 6: DISTILLATION. K-38, MIDC Butibori, Nagpur, Maharashtra.

86

NODE 6 : DISTILLATION. EQUIPMENT: DISTILLATION SYSTEM. DESIGN INTENT : Solvent Recovery.

GUIDE WORD



Loss of cooling medium at condenser.

More flow at condenser vent.

SOP. Supervision.

4 3 12



SOP. Supervision.

4 3 12

Reverse.

Flow. Reverse flow. Power failure during recovery of solvent by vacuum distillation.

Ingress of air to hot flammable solvent in the distillation system. Fire/ explosion hazard.

SOP. Supervision.

3 3 9 Provide Nitrogen for breaking vacuum during solvent recovery by distillation.

As Well As.

Emissions. Vent gases. VOC. Environmental issues. SOP. Supervision.

3 3 9 Verify the condenser capacity so that solvent loss from the system during reflux will be minimized. Provide temperature controller for steam line at hot water system.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 6: DISTILLATION. K-38, MIDC Butibori, Nagpur, Maharashtra.

87

NODE 6 : DISTILLATION. EQUIPMENT: DISTILLATION SYSTEM. DESIGN INTENT : Solvent recovery

GUIDE WORD


Other. Flow. Static charge. Handling of static sensitive material.

Static charge as source of ignition, fire hazard.




Excessive heating. Emission at vent. TI. Supervision.

3 3 9 Provide temperature controller for steam line at hot water system.

More. Pressure. More pressure. Excessive heating when low boiling solvent inside.

Pressurization. SOP. Supervision.

4 3 12 Provide SRV on the jacket of the reactors handling low boiling solvents.

More. Phase. More phases. Gas, liquid phases. Not significant. – – – – –

As Well As.

Composition. Impurities. Accumulation of impurities in residue.

Explosion hazard. Process control. Supervision.

5 3 15 Avoid recovery to dryness, keep mobility of residue.





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


SOP. Supervision.

2 2 4

88

Unit processes and unit operations not covered earlier are studied under this node. And

significant hazardous events are recorded. Typical unit operations considered are as

follows:

Absorption.

Adsorption.

Apparatus Cleaning.

Centrifugation.

Charging Reactants & Solvents.

Crystallisation.

Discharging.

Distillation (considered under Node 6).

Drying.

Evaporation.

Extraction.

Filtration.

Fractionation.

Inerting.

Milling.

Mixing.

Phase Separation.

Precipitation.

Product Washing.

Quenching.

Separation.

Stripping.

Ultra Filtration.

Charcoal Treatment.

M/S. INVENTYS RESEARCH CO. PVT. LTD. NODE 7: OTHERS. K-38, MIDC Butibori, Nagpur, Maharashtra.

89

NODE 7 : OTHERS UNIT OPERATIONS AND OTHER UNIT PROCESSES. DESIGN INTENT : RECEIPT, STORAGE AND HANDLING.

GUIDE WORD


None. Flow. No flow. No flow of cooling medium to reactor.

Uncontrolled reaction.Pressurization / explosion hazard.

SOP. Supervision.

4 3 12


Loss of cooling medium at condenser.

More flow at condenser vent.

SOP. Supervision.

4 3 12



SOP. Supervision.

4 3 12

Reverse. Flow. Reverse flow. Power failure during recovery of solvent by vacuum distillation.

Ingress of air to hot flammable solvent in the distillation system. Fire/ explosion hazard.

SOP. Supervision.

3 3 9 Provide Nitrogen for breaking vacuum during solvent recovery by distillation.

As Well As.

Effluent. Effluent generation.

Mother liquor. Washings.

Environmental issues. ETP provided. 3 3 9 The waste stream containing cyanide should be collected and segregated for disposal, Cyanide destroyed completely before discharge.

As Well As.

Emissions. Vent gases. VOC. Environmental issues. SOP. Supervision.

3 3 9 Verify the condenser capacity so that solvent loss from the system during reflux will be minimized. Provide temperature controller for steam line at hot water system.


90


GUIDE WORD


As Well As.

Solid waste.

Solid waste generation.

Spent catalyst. Residue.

Environmental issues. Hazardous solid waste disposal to CHWTSDF.

3 3 9

Other. Flow. Static charge. Handling of static sensitive material.

Static charge as source of ignition, fire hazard.




Excessive heating. Emission at vent. TI. Supervision.

3 3 9 Provide temperature controller for steam line at hot water system.


Excessive cooling. Freezing, disturbed operation.

3 1 3

More. Pressure. More pressure. Excessive heating when low boiling solvent inside reactor.

Pressurization. SOP. Supervision.

4 3 12 Provide SRV on the jacket of the reactors handling low boiling solvents.

Less. Pressure. Less pressure. Vacuum in the system. Fast pumping out and vent closed. Fast cooling, vent closed.

Not significant. Equipments are designed for vacuum.

3 3 9


91


GUIDE WORD


As Well As.

Composition. Contamination. Unreacted Cyanide in reaction mass.

Health hazard in handling down stream operations.

Process control. Supervision.

3 3 9 Consider use of stichometric quantities of Cyanide in the reaction to ensure the down stream equipments are free from Cyanide and reduction in the quantity of effluent generated.





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


SOP. Supervision.

2 2 4

Other. Handling. Handling of Cyanides.

Release of Hydrogen Cyanide during handling of Cyanides.

Health hazard in handling down stream operations.

SOP. Supervision.

3 3 9 Provide Hydrogen Cyanide leak detector at strategic locations at the plant during the Cyanide handling products. Provide cyanide kit.

Other. Handling. Handling low boiling solvents.

MDC handling. Health hazard. SOP. Supervision.

4 3 12 Avoid transfer of volatile solvents such as Di Chloro Methane by vacuum. Consider AODP, peristaltic pump for transfer of volatile solvents.


92


GUIDE WORD


Other. Handling. Powders handling.

Safety class of the powder handled not known.

Dust explosion hazard.

SOP. Supervision. Equipments are earthed.

3 3 9 The reactions that occur when a solid heats and ignition starts are far more complicated than for a gas and may include oxidation, decomposition, melting and vaporisation. The result is that the flammability and ignitability of a dust can only be characterized after suitable tests. Carry out dust safety tests and utilize the data while equipment selection and operation.

Other. Handling. Powders handling.

Drying, FBD operations.

Dust explosion hazard.

SOP. Supervision. Equipments are earthed.

3 3 9 Provide explosion vent to dryer.

93

ANNEXURE 1: COMPATIBILITY/ REACTIVITY HAZARDS (Of chemicals unintended mix up)

1.1 COMPATIBILITY HAZARDS FOR THE FOLLOWING LIST OF REACTANTS

1) ACETONITRILE 2) BROMINE 3) CHLORO SULFONIC ACID 4) DI ISO PROPYL ETHER 5) N-HEXANE 6) NITRIC ACID, FUMING 7) SODIUM CYANIDE 8) TERT-BUTYL ALCOHOL 9) TRI ETHYL AMINE

1.2 HAZARD SUMMARY FOR ALL POSSIBLE PAIRINGS OF CHEMICALS

Risk of explosion by shock, friction, fire or other sources of ignition. Forms very unstable explosive metallic compounds. Reaction proceeds with explosive violence and/or forms explosive products. Explosive when mixed with combustible material. Heat generated from chemical reaction may initiate explosion. May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Spontaneous ignition of reactants or products due to reaction heat. Combination liberates gaseous products, at least one of which is flammable.

May cause pressurization. Combination liberates gaseous products, including both flammable and toxic

gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization. Exothermic, potentially violent polymerization. May cause pressurization. Combination liberates gaseous products, at least one of which is toxic. May

cause pressurization. Generates water soluble toxic products. Reaction may be intense or violent.

1.3 HAZARD STATEMENTS FOR EACH POSSIBLE PAIRING OF CHEMICALS

ACETONITRILE

mixed with

BROMINE Reaction proceeds with explosive violence and/or forms explosive

products. May become highly flammable or may initiate a fire, especially if other

combustible materials are present.

94

Combination liberates gaseous products, including both flammable and toxic gases. May cause pressurization.

Exothermic reaction. May generate heat and/or cause pressurization. Exothermic, potentially violent polymerization. May cause

pressurization. CHLORO SULFONIC ACID Reaction proceeds with explosive violence and/or forms explosive

products. Spontaneous ignition of reactants or products due to reaction heat. Combination liberates gaseous products, including both flammable

and toxic gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization. Exothermic, potentially violent polymerization. May cause

pressurization. DI ISO PROPYL ETHER No reaction expected

N-HEXANE No reaction expected

NITRIC ACID, FUMING Reaction proceeds with explosive violence and/or forms explosive

products. Spontaneous ignition of reactants or products due to reaction heat. Combination liberates gaseous products, including both flammable

and toxic gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization. Exothermic, potentially violent polymerization. May cause

pressurization. SODIUM CYANIDE No reaction expected

TERT-BUTYL ALCOHOL No reaction expected

TRI ETHYL AMINE No reaction expected

BROMINE

mixed with

CHLORO SULFONIC ACID Reaction proceeds with explosive violence and/or forms explosive

products.

95

Explosive when mixed with combustible material. Heat generated from chemical reaction may initiate explosion. Spontaneous ignition of reactants or products due to reaction heat. Combination liberates gaseous products, including both flammable

and toxic gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. DI ISO PROPYL ETHER Risk of explosion by shock, friction, fire or other sources of ignition. Reaction proceeds with explosive violence and/or forms explosive

products. Explosive when mixed with combustible material. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. Reaction may be intense or violent.

N-HEXANE Reaction proceeds with explosive violence and/or forms explosive

products. Heat generated from chemical reaction may initiate explosion. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization.


products. Explosive when mixed with combustible material. Heat generated from chemical reaction may initiate explosion. Spontaneous ignition of reactants or products due to reaction heat. Combination liberates gaseous products, including both flammable

and toxic gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. SODIUM CYANIDE Reaction proceeds with explosive violence and/or forms explosive

products. May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.


96

TERT-BUTYL ALCOHOL Forms very unstable explosive metallic compounds. Reaction proceeds with explosive violence and/or forms explosive

products. Heat generated from chemical reaction may initiate explosion. May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. TRI ETHYL AMINE Forms very unstable explosive metallic compounds. Reaction proceeds with explosive violence and/or forms explosive

products. Heat generated from chemical reaction may initiate explosion. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. Reaction may be intense or violent.

CHLORO SULFONIC ACID

mixed with

DI ISO PROPYL ETHER Reaction proceeds with explosive violence and/or forms explosive

products. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization. Generates water soluble toxic products.

N-HEXANE May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Exothermic reaction. May generate heat and/or cause pressurization. Combination liberates gaseous products, at least one of which is toxic.

May cause pressurization. NITRIC ACID, FUMING No reaction expected

SODIUM CYANIDE Reaction proceeds with explosive violence and/or forms explosive

products. Exothermic reaction. May generate heat and/or cause pressurization.

97

Combination liberates gaseous products, including both flammable and toxic gases. May cause pressurization.

TERT-BUTYL ALCOHOL Heat generated from chemical reaction may initiate explosion. May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Combination liberates gaseous products, at least one of which is

flammable. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization.

TRI ETHYL AMINE Reaction proceeds with explosive violence and/or forms explosive



DI ISO PROPYL ETHER

mixed with

N-HEXANE No reaction expected


products. Spontaneous ignition of reactants or products due to reaction heat. Exothermic reaction. May generate heat and/or cause pressurization. Generates water soluble toxic products.

SODIUM CYANIDE No reaction expected



N-HEXANE

mixed with

NITRIC ACID, FUMING Exothermic reaction. May generate heat and/or cause pressurization.

98

May become highly flammable or may initiate a fire, especially if other combustible materials are present.

Combination liberates gaseous products, at least one of which is toxic. May cause pressurization.

SODIUM CYANIDE No reaction expected



NITRIC ACID, FUMING

mixed with

SODIUM CYANIDE Reaction proceeds with explosive violence and/or forms explosive

products. Combination liberates gaseous products, including both flammable

and toxic gases. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization.

TERT-BUTYL ALCOHOL Heat generated from chemical reaction may initiate explosion. May become highly flammable or may initiate a fire, especially if other

combustible materials are present. Combination liberates gaseous products, at least one of which is

flammable. May cause pressurization. Exothermic reaction. May generate heat and/or cause pressurization.

TRI ETHYL AMINE Reaction proceeds with explosive violence and/or forms explosive



SODIUM CYANIDE

mixed with


99


TERT-BUTYL ALCOHOL

mixed with

TRI ETHYL AMINE Exothermic reaction. May generate heat and/or cause pressurization.

100

ANNEXURE 2: HAZOP METHODOLOGY

HAZOP

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

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

now used to great satisfaction throughout the chemical Industries.

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

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

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

final design phase and during modifications of the existing plants.

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

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

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

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

consequences.

101

DATA COLLECTION

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

HAZOP COMMITTEE

The HAZOP committee is formed as per following guidelines

CHAIRMAN OCCUPIER / FACTORY MANAGER.

CO –ORDINATOR Safety officer.

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

PROJECT or DESIGN ENGINEER For a new design MAINTENANCE MANAGER For operating plant

Usually a mechanical engineer and, at this stage of the project, the person responsible for keeping the costs within the sum sanctioned. He wants to minimize changes but at the same time wants to find out rather than later if there are any unknown hazards or operating problems.

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

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

INSTRUMENT /DESIGN ENGINEER

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

RESEARCH CHEMIST If new chemistry is involved. STUDY PROCEDURE

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

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

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

opposites all conceivable eventualities.

102

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

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

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

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

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

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

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

analysis is also carried out.

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

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

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

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

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

members have the necessary background knowledge of the process.

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

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

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

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

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

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

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

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

MEANING OF THE GUIDE WORDS

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

letters):

NONE: No flow, reverse flow, i.e. no forward flow when there should be.

MORE OF: More of flow, temperature, pressure, viscosity etc. higher flow, higher

temperature, or whatsoever than there should be.

LESS OFF: Lower flow, temperature, pressure, Viscosity, etc. than there should be.

103

PART OF: Changes in compositions of the stream, e.g. ratio of components different from what it should be.

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

vapor, solids.

OTHER: What else part from normal operations can happen, e.g. start-up, shutdown,

maintenance, catalyst change, failure of plant services.

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

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

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

assessment.

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

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

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

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

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

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

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

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

recommended considering the probability and seriousness of the hazard Recommendations

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

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

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

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

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

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

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

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

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

enough etc.)

104

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

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

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

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

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

occasionally or every probable).

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

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

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

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

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

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

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

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

should again be recorded for attention outside the meeting.

DOCUMENTATION

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

details:

HAZOP STUDY

: This consist of description in short of the process used or the manufacture of final product.

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

P & I REFERENCE : This refers to the concerned P & I drawing number used for particular operating step.

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

DESIGN INTENTION : This actually is the sub step which describes the intention of the sub step.

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

GUIDE WORD : These are the words which are to be applied to intentions for asking questions for deviations. These are already well explained in above portion of this chapter. There can be many deviation.

CAUSE (S)

: Each of the deviation as mentioned above can have many causes. These are mentioned in front of that deviation.

105

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

S/P/R : For each cause there is specified probability and seriousness associated with each deviation. The probability an seriousness individually needs to be judged quantitatively on the predetermined scale. Considering the level of consequences from 1 to 5 and probability levels as 1 to 5 determined by safety philosophy and past experience of the HAZOP committee arrive at risk value index of level 1 to 10 for each identified hazard. The highest is indicated in the scale used.

ACTION : This is very important aspect and needs detail consideration. The actions are to be suggested for all those consequences except which fall as low class as far as probability and seriousness are concerned. While considering actions many points are to be debated to find a solution which is cost effective and removes root cause, so that the deviation does not occur or at lest it reduces the probability and/or seriousness.

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

OPEN QUESTIONS : In this column as mentioned in the earlier portion of the chapter, if further study is to be done it has to be mentioned as to what is expected from the experiments/data to be collected. Few can be done immediately as in our case or few may need longer period of experimenting. Thus the total work sheet is filled as described above and documented in. Further for each step, there is a need to have a summary sheet of the actions to be taken. These needs to be summarized in a single sheet as 'Recommendations from “HAZOP”. Here detail description of the weakness observed during the study and the recommendations made are described. This helps management to get a view of the study in a nutshell without going through the volume of Hazard worksheets. Many actions on worksheet are repeated & hence one can cover many deviations on one sheet.

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

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

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

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

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

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

copies were used for the “HAZOP” study.

106

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

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

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

the table work of conducting the study. The documentation indicates;

Which segment of process or procedure were reviewed?

Which guide words & parameters were considered?

The cause and consequences of each deviation studied.

Whether a potential problem exists?

What are the existing safeguards?

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

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

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

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

documented as “HAZOP WORKSHEET”.

STUDY RESULTS/ FINDINGS

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

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

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

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

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

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

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

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

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

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

recorded.

107

ANNEXURE 3: MSDS HIGHLIGHTS

ACETIC ACID Synonyms Acetic Acid-Glacial, Methane Carboxylic Acid;

Ethanoic Acid. Chemical Formula CH3 COOH CAS No. 64-19-7 Molecular Weight 60.05

Emergency Overview Poison! Danger! Corrosive. Liquid and mist cause severe burns to all body

tissue. May be fatal if swallowed. Harmful if inhaled. Inhalation may cause

lung and tooth damage. Flammable liquid and vapor.

Inhalation Inhalation of concentrated vapors may cause serious damage to the lining of

the nose, throat, and lungs. Breathing difficulties may occur. Neither odor nor

degree of irritation are adequate to indicate vapor concentration

Ingestion Swallowing can cause severe injury leading to death. Symptoms include sore

throat, vomiting, and diarrhea. Ingestion of as little as 1.0 ml has resulted in

perforation of the esophagus.

Skin Contact Contact with concentrated solution may cause serious damage to the skin.

Effects may include redness, pain, skin burns. High vapor concentrations may

cause skin sensitization.

Eye Contact Eye contact with concentrated solutions may cause severe eye damage

followed by loss of sight. Exposure to vapor may cause intense watering and

irritation to eyes.

Chronic Exposure Repeated or prolonged exposures may cause darkening of the skin, erosion of

exposed front teeth, and chronic inflammation of the nose, throat, and

bronchial tubes.

Fire Flash point: 40C (104F) CC

Autoignition temperature: 427C (801F),Flammable limits in air % by volume:

lel: 4.0; uel: 16.0 Flammable Liquid and Vapor!

Explosion Above flash point, vapor-air mixtures are explosive within flammable limits

noted above. Vapors can flow along surfaces to distant ignition source and

flash back. Contact with strong oxidizers may cause fire. Reacts with most

metals to produce hydrogen gas, which can form an explosive mixture with

air.

108

ACETIC ACID Synonyms Acetic Acid-Glacial, Methane Carboxylic Acid;

Ethanoic Acid. Chemical Formula CH3 COOH CAS No. 64-19-7 Molecular Weight 60.05

Stability Stable under ordinary conditions of use and storage. Heat and sunlight can

contribute to instability. Releases heat and toxic, irritating vapors when mixed

with water. Acetic acid contracts slightly upon freezing which may cause the

container to burst.

Conditions To Avoid Heat, flame, ignition sources, freezing, incompatibles

Hazardous

Decomposition Products

Carbon dioxide and carbon monoxide may form when heated to decomposition.

May also release toxic and irritating vapors.

Incompatibilities Acetic Acid is incompatible with chromic acid, nitric acid, ethylene glycol,

perchloric acid, phosphorous trichloride, oxidizers, sodium peroxide, strong

caustics, most metals (except aluminum), carbonates, hydroxides, oxides, and

phosphates.

Toxicity Oral rat LD50: 3310 mg/kg; skin rabbit LD50: 1.06 g/kg; inhalation mouse

LC50: 5620ppm/1-hr; investigated as a mutagen, reproductive effector.

Airborne Exposure

Limits

OSHA Permissible Exposure Limit (PEL): 10 ppm (TWA).

ACGIH Threshold Limit Value (TLV): 10 ppm (TWA); 15 ppm (STEL).

Environmental Fate When released into the air, this material may be moderately degraded by

reaction with photochemically produced hydroxyl radicals. When released into

air, this material is expected to have a half-life between 10 and 30 days. When

released into water, this material is expected to readily biodegrade. When

released into the water, this material is expected to have a half-life between 1

and 10 days. Standard dilution BOD5/TOD = 58% When released into the

soil, this material is expected to readily biodegrade. This material is not

expected to significantly bioaccumulate. This material has an estimated

bioconcentration factor (BCF) of less than 100.

Environmental

Toxicity

This material is expected to be slightly toxic to aquatic life. The LC50/96-hour

values for fish are between 10 and 100 mg/l.

NFPA Ratings Health: 3 Flammability: 2 Reactivity: 0

109

ACRYLONITRILE Synonyms Acrylonitrile monomer; 2-Propenenitrile; Vinyl

cyanide; Cyanoethylene. Chemical Formula C3 H3 N CAS No. 107-13-1 Molecular Weight 53.06

Emergency Overview Danger! May be fatal if inhaled, absorbed through the skin or swallowed. Flammable liquid and vapor. Causes eye, skin, and respiratory tract irritation. May cause allergic skin reaction. May cause cancer based on animal studies. This material has been reported to be susceptible to autoxidation and therefore should be classified as peroxidizable. Light sensitive. Hazardous polymerization may occur. Hazardous due to peroxide initiation of polymerization.

Inhalation May be fatal if inhaled. Inhalation of high concentrations may cause central nervous system effects characterized by nausea, headache, dizziness, unconsciousness and coma. May cause cyanosis (bluish discoloration of skin due to deficient oxygenation of the blood). Causes respiratory tract irritation. Exposure to high concentrations may cause weakness, asphyxia, and death. May be metabolized to cyanide which in turns act by inhibiting cytochrome oxidase impairing cellular respiration. Material volatilizes at room temperature.

Ingestion May be fatal if swallowed. Acrylonitrile forms very toxic cyanide in the body, but to a lesser extent than some other nitriles. There is a relatively low rate of conversion of acrylonitrile to cyanide (approximately 20% following oral exposure).

Skin Contact Causes skin irritation. Harmful if absorbed through the skin. May cause skin sensitization, an allergic reaction, which becomes evident upon re-exposure to this material. Causes symptoms similar to those of inhalation.

Eye Contact Causes severe eye irritation. May result in corneal injury. Lachrymator (substance which increases the flow of tears). Causes redness and pain.

Chronic Exposure Acrylonitrile has caused nervous system effects (e.g. reduced nerve conduction) in animals exposed to very low concentrations, which have also been associated with the development of nervous system cancer. Inhalation of relatively low concentrations of acrylonitrile (20 ppm for 24 months) has caused degeneration and inflammatory changes in the nasal cavities of rats

Fire Flash Point: -5 deg C ( 23.00 deg F). Autoignition Temperature: 481 deg C (897.80 deg F). Explosion Limits, Lower:3.1%. Upper: 17.0%.

Explosion Fire or excessive heat may result in violent rupture of the container due to bulk polymerization. Vapors are heavier than air and may travel to a source of ignition and flash back. Vapors can spread along the ground and collect in low or confined areas.

Stability Acrylonitrile vapor or uninhibited liquid may polymerize explosively, if heated, or exposed to sunlight (ultraviolet light), pressure, peroxides, or other incompatible materials. Inhibited liquid may polymerize explosively at temperatures > 200°C.

Hazardous Polymerization

May occur.

Conditions To Avoid Light, ignition sources, excess heat, loss of inhibitor, confined spaces.

110

ACRYLONITRILE Synonyms Acrylonitrile monomer; 2-Propenenitrile; Vinyl

cyanide; Cyanoethylene. Chemical Formula C3 H3 N CAS No. 107-13-1 Molecular Weight 53.06

Hazardous Decomposition Products

Hydrogen cyanide, nitrogen oxides, carbon monoxide, carbon dioxide.

Incompatibilities Strong bases, strong acids, halogens, amines, strong oxidizing agents, polymerizing initiators.

Toxicity Dermal, guinea pig: LD50 = 202 mg/kg; Draize test, rabbit, eye: 100 mg Moderate; Draize test, rabbit, skin: 500 mg Severe; Inhalation, rat: LC50 = 333 ppm/4H;

Airborne Exposure Limits

Acrylonitrile 2 ppm TWA; Skin - potential significant contribution to overall exposure by the cutaneous route 1 ppm TWA 85 ppm IDLH 2 ppm TWA; 10 ppm Ceiling; 1 ppm Action Level; 2 ppm TWA; 10 ppm Excursion Limit (15 min, Skin and eye expo sure prohibited.

Environmental Toxicity

Aquatic: Reacts to produce 3-hydroxypropionitrile and bis(2-cyanoethyl)ether in the presence of a catalyst. Terrestrial: Expected to evaporate rapidly if spilled on land. Because it is so poorly adsorbed to soil, it may also leach. Atmospheric: Will degrade by reaction with hydroxyl radicals; half-life of 3.5 12-hr sunlit days. The biodegradation is reported to occur readily at concentrations > 20 mg/l during anaerobic digestion process. Experimental and estimated factors indicate that bioconcentration in aquatic organisms is not significant.

NFPA Ratings Health: 4; Flammability: 3; Instability: 2

111

BROMINE Synonyms Brom. Chemical Formula Br2 CAS No. 7726-95-6 Molecular Weight 159.8

Emergency Overview Danger! Corrosive. May be fatal if swallowed or inhaled. Causes severe burns to every area of contact. Affects respiratory system, eyes, central nervous system and skin. Strong oxidizer. Contact with other material may cause fire.

Inhalation Both liquid and vapor are corrosive to all body tissues and may cause serious burns. Excessive inhalation of vapors may be very irritating and damaging to the respiratory tract and lungs. Symptoms include headache, cough, nosebleed, vertigo, pulmonary edema, and abdominal pain.

Ingestion Corrosive! Sore throat, vomiting and abdominal spasms may occur. Estimated lethal dose: l4 mg/kg.

Skin Contact Corrosive! Symptoms may include skin discoloration, pain, serious burns, blistering, and slow healing ulcers.

Eye Contact Corrosive. Can cause blurred vision, redness, pain, severe tissue burns and eye damage.

Chronic Exposure Pulmonary edema, pneumonia, diarrhea, and rashes may be delayed complications of severe exposures.

Fire Not combustible, but substance is a strong oxidizer and its heat of reaction with reducing agents or combustibles may cause ignition. Highly toxic and dense fumes are emitted when bromine is heated. Vapors can flow along surfaces to low lying areas.

Explosion Not considered to be an explosion hazard. Stability Stable under ordinary conditions of use and storage. Conditions To Avoid Moisture, heat, flames, ignition sources and incompatibles. Avoid direct

sunlight. Hazardous Decomposition Products

Emits fumes of Bromine and Bromides upon thermal decomposition. Hydrogen Bromide is a by-product of many bromine reactions.

Incompatibilities Will react with steam or water to produce toxic and corrosive fumes of hypobromous acid and hydrogen bromide. Attacks most metals, reacting violently with aluminum, titanium, mercury, and potassium. Incompatible with reducing agents, combustibles, and many organic chemicals.

Toxicity Oral rat LD50: 2600 mg/kg; Inhalation rat LC50: 2700 mg/m3. Airborne Exposure Limits

OSHA Permissible Exposure Limit (PEL): 0.1 ppm (TWA). ACGIH Threshold Limit Value (TLV): 0.1 ppm (TWA), 0.2 ppm (STEL).

Environmental Fate When released into the air, this material is expected to adversely affect the ozone layer.


This material is expected to be toxic to aquatic life.

NFPA Ratings Health: 4 Flammability: 0 Reactivity: 0 Other: Oxidizer

112

CHLORO SULFONIC ACID Synonyms Chlorosulfonic acid, 98%.

Chemical Formula Cl S O3 H

CAS No. 7790-94-5 Molecular Weight 116.52

Emergency Overview Absorbs moisture from the air.

Inhalation Causes respiratory tract irritation. Causes chemical burns to the respiratory

tract.

Ingestion Causes gastrointestinal tract burns.

Skin Contact Causes skin burns.

Eye Contact Causes eye burns. Lachrymator (substance which increases the flow of tears).

Chronic Exposure Not available.

Fire Do not use water directly on fire.

Explosion Explosion Limits, Lower:3.30 vol % Upper: 37.70 vol %

Stability Chemical Stability: Stable under normal temperatures and pressures.

Conditions To Avoid Incompatible materials, organic materials.

Hazardous Decomposition Products

Hydrogen chloride, oxides of sulfur.

Incompatibilities Water, metals, acids, bases, alcohols, amines, finely powdered metals,

plastics.

Toxicity LD50/LC50: Oral, rat: LD50 = 50 mg/kg;


No data available.


No data available.

NFPA Ratings Health: 4; Flammability: 0; Instability: 2.

113

Di ISO PROPYL ETHER Synonyms Diisopropylether; Diisopropyl Oxide; 2-

Isopropoxypropane;2-2'-oxybispropane. Chemical Formula (CH3)2CHOCH(CH3)2 CAS No. 108-20-3 Molecular Weight 102.18

Emergency Overview Danger! Extremely flammable liquid and vapor. Vapor may cause flash fire. Harmful if swallowed, inhaled or absorbed through skin. Causes irritation to skin, eyes and respiratory tract. Affects central nervous system.

Inhalation Causes irritation of the respiratory tract and mucous membranes. Higher concentrations may produce an narcotic effect.

Ingestion Large oral doses may cause an anesthetic effect and central nervous system depression.

Skin Contact Causes irritation. Symptoms include redness, itching, and pain. May be absorbed through the skin to produce symptoms paralleling ingestion.

Eye Contact Vapors and liquid cause irritation, redness, and pain. Chronic Exposure Prolonged or repeated skin exposure may cause dermatitis and drying of skin.Fire Flash point: -27.8C (-18F) CC. Autoignition temperature: 443C (829F).

Flammable limits in air % by volume: lel: 1.4; uel: 7.9. Extremely Flammable. Explosion Above flash point, vapor-air mixtures are explosive within flammable limits

noted above. Vapors can flow along surfaces to distant ignition source and flash back. May form unstable peroxides which may explode spontaneously or when heated. Sealed containers may rupture when heated. Sensitive to static discharge.

Stability Stabilized with approx. 0.01% BHT Unstabilized material: contact with air may form explosive peroxides that may detonate when heated or shocked.

Conditions To Avoid Heat, flames, ignition sources and incompatibles. Hazardous Decomposition Products

Carbon dioxide and carbon monoxide may form when heated to decomposition.

Incompatibilities Air, oxygen, chlorosulfonic acid, nitric acid. Contact with oxidizers may cause explosions or fire.

Toxicity Oral rat LD50: 8470 mg/kg. Skin rabbit LD50: 20ml/kg. Inhalation rat LD50: 162 gm/m3. Irritation data: skin rabbit 363 mg open - mild.


OSHA Permissible Exposure Limit (PEL): 500 ppm (TWA) ACGIH Threshold Limit Value (TLV):250 ppm (TWA), 310 ppm (STEL)

Environmental Fate When released into the soil, this material may leach into groundwater, this material is expected to quickly evaporate. When released into water, this material is not expected to biodegrade this material is expected to quickly evaporate, this material is expected to have a half-life between 1 and 10 days. This material has an experimentally-determined bioconcentration factor (BCF) of less than 100. This material has a log octanol-water partition coefficient of less than 3.0. When released into the air, this material is expected to be readily degraded by reaction with photochemically produced hydroxyl radicals, this material is not expected to be degraded by photolysis, this material is expected to have a half-life of less than 1 day.


The LC50/96-hour values for fish are between 10 and 100 mg/l.


114

HEXANE Synonyms Hexanes,Normal Hexane;Hexyl Hydride;Hexane 95%. Chemical Formula CH3(CH2)4 CH3 CAS No. 110-54-3 Molecular Weight 86.18

Emergency Overview Danger! Extremely flammable liquid and vapor. Vapor may cause flash fire.

Harmful or fatal if swallowed. Harmful if inhaled. Causes irritation to skin,

eyes and respiratory tract. Affects the central and peripheral nervous systems.

Inhalation The health hazards addressed are for the major component: n-hexane.

Inhalation of vapors irritates the respiratory tract. Overexposure may cause

lightheadedness, nausea, headache, and blurred vision. Greater exposure may

cause muscle weakness, numbness of the extremities, unconsciousness and

death.

Ingestion May produce abdominal pain, nausea. Aspiration into lungs can produce

severe lung damage and is a medical emergency. Other symptoms expected to

parallel inhalation.

Skin Contact May cause redness, irritation, with dryness, cracking.

Eye Contact Vapors may cause irritation. Splashes may cause redness and pain.

Chronic Exposure Repeated or prolonged skin contact may defat the skin and produce irritation

and dermatitis. Chronic inhalation may cause peripheral nerve disorders and

central nervous system effects.

Aggravation of Pre-

existing Conditions

Persons with pre-existing skin disorders or eye problems or impaired

respiratory function may be more susceptible to the effects of the substance.

May affect the developing fetus.

Fire Flash point: -23C (-9F) CC. Autoignition temperature: 224C (435F). Flammable

limits in air % by volume: lel: 1.2; uel: 7.7. Extremely Flammable Liquid and

Vapor! Vapor may cause flash fire. Dangerous fire hazard when exposed to

heat or flame.

Explosion Above flash point, vapor-air mixtures are explosive within flammable limits

noted above. Contact with oxidizing materials may cause extremely violent

combustion. Explodes when mixed @ 28C with dinitrogen tetraoxide. Sensitive

to static discharge.

115

HEXANE Synonyms Hexanes,Normal Hexane;Hexyl Hydride;Hexane 95%. Chemical Formula CH3(CH2)4 CH3 CAS No. 110-54-3 Molecular Weight 86.18

Stability Stable under ordinary conditions of use and storage. Heat will contribute to

instability.

Hazardous

Polymerization

Will not occur.

Conditions To Avoid Heat, flames, ignition sources and incompatibles.

Hazardous

Decomposition Products

May produce acrid smoke and irritating fumes when heated to decomposition.

Incompatibilities Strong oxidizers.

Toxicity N-Hexane: Oral rat LD50: 28710 mg/kg. Irritation eye rabbit: 10 mg mild.

Investigated as a tumorigen, mutagen and reproductive effector.

Airborne Exposure

Limits

OSHA Permissible Exposure Limit (PEL): 500 ppm (TWA)-ACGIH Threshold

Limit Value (TLV): 50 ppm (TWA), Skinother isomers of hexane-ACGIH

Threshold Limit Value (TLV): 500 ppm (TWA),1000ppm (STEL)

Environmental Fate When released into the soil, this material may biodegrade to a moderate extent. When released into the soil, this material is not expected to leach into groundwater. When released into the soil, this material is expected to quickly evaporate. When released into water, this material may biodegrade to a moderate extent. When released to water, this material is expected to quickly evaporate. When released into the water, this material is expected to have a half-life between 1 and 10 days. This material has an estimated bioconcentration factor (BCF) of less than 100. This material has a log octanol-water partition coefficient of greater than 3.0. This material is not expected to significantly bioaccumulate. When released into the air, this material is expected to be readily degraded by reaction with photochemically produced hydroxyl radicals. When released into the air, this material is expected to have a half-life between 1 and 10 days.


116

NITRIC ACID 98 % Synonyms Aqua Fortis; Azotic Acid; Red fuming nitric

acid. Chemical Formula H N O3 CAS No. 7697-37-2 Molecular Weight 63

Emergency Overview Poison! Danger! Strong oxidizer. Contact with other material may cause fire. Corrosive. Liquid and mist cause severe burns to all body tissue. May be fatal if swallowed or inhaled. Inhalation may cause lung and tooth damage.

Inhalation Corrosive! Inhalation of vapors can cause breathing difficulties and lead to pneumonia and pulmonary edema, which may be fatal. Other symptoms may include coughing, choking, and irritation of the nose, throat, and respiratory tract. Symptoms may disappear only to return in a few hours and more severely. Onset of symptoms may be delayed for 4-30 hours.

Ingestion Corrosive! Swallowing nitric acid can cause immediate pain and burns of the mouth, throat, esophagus and gastrointestinal tract.

Skin Contact Corrosive! Can cause redness, pain, and severe skin burns. Concentrated solutions cause deep ulcers and stain skin a yellow or yellow-brown color.

Eye Contact Corrosive! Vapors are irritating and may cause severe damage to the eyes. Splashes may cause severe burns and permanent eye damage.

Chronic Exposure Long-term exposure to concentrated vapors may cause erosion of teeth and lung damage. Long-term exposures seldom occur due to the corrosive properties of the acid.

Fire Not combustible, but substance is a strong oxidizer and its heat of reaction with reducing agents or combustibles may cause ignition. Can react with metals to release flammable hydrogen gas.

Explosion Reacts explosively with combustible organic or readily oxidizable materials such as: alcohols, turpentine, charcoal, organic refuse, metal powder, hydrogen sulfide, etc. Reacts with most metals to release hydrogen gas which can form explosive mixtures with air.

Stability Stable under ordinary conditions of use and storage. Containers may burst when heated.

Conditions To Avoid Heat, light, moisture. Hazardous Decomposition Products

When heated to decomposition, emits toxic nitrogen oxides fumes and hydrogen nitrate. Will react with water or steam to produce heat and toxic and corrosive fumes.

Incompatibilities A dangerously powerful oxidizing agent, fuming nitric acid is incompatible with most substances, especially strong bases, metallic powders, carbides, hydrogen sulfide, turpentine, and combustible organics.

Toxicity For Nitric Acid: Oral (human) LDLo: 430 mg/kg; Inhalation,rat, LC50: 67 ppm (NO2)/4H.; Investigated as a mutagen and reproductive effector.


-OSHA Permissible Exposure Limit (PEL): 2 ppm (TWA), 4 ppm (STEL) -ACGIH Threshold Limit Value (TLV): 2 ppm (TWA); 4 ppm (STEL)


No information found.

NFPA Ratings Health: 4 Flammability: 0 Reactivity: 1 Other: Oxidizer.

117

SODIUM CYANIDE

Synonyms Hydrocyanic acid, sodium salt; Cyanogran. Chemical Formula Na C N CAS No. 143-33-9 Molecular Weight 49.01

Emergency Overview Danger! May be fatal if swallowed, inhaled or absorbed through skin. Contact with acids liberates poisonous gas. Causes burns to skin, eyes, and respiratory tract. Affects blood, cardiovascular system, central nervous system and thyroid.

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

Ingestion Highly Toxic! Corrosive to the gastro-intestinal tract with burning in the mouth and esophagus, and abdominal pain. Larger doses may produce sudden loss of consciousness and prompt death from respiratory arrest. Smaller but still lethal doses may prolong the illness for one or more hours. Bitter almonds odor may be noted on the breath or vomitus.

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

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

Chronic Exposure Prolonged or repeated skin exposure may cause a "cyanide" rash and nasal sores.

Fire Not combustible, but upon decomposition or contact with acids, this material releases highly flammable and toxic hydrogen cyanide gas.

Explosion Not considered an explosion hazard, but upon heating with chlorates or nitrites to 450C (842F) may cause an explosion. Violent explosion occurs if melted with nitrite salt. Sealed containers may rupture when heated.

Stability Very stable when dry. Moisture will cause slow decomposition, releasing poisonous hydrogen cyanide gas.

Conditions To Avoid Heat, moisture, incompatibles. Hazardous Decomposition Products

Emits toxic fumes of cyanide and oxides of nitrogen when heated to decomposition.

Incompatibilities Acid. nitrates, nitrites, chlorates, fluorine, magnesium, and strong oxidizers. Reacts with acids to liberate toxic and flammable hydrogen cyanide gas. Water or weak alkaline solutions can produce dangerous amounts of hydrogen cyanide in confined areas.Reacts with CO2 in air to form hydrogen cyanide gas.

Toxicity Oral rat LD50: 6440 ug/kg. Investigated as a tumorigen, mutagen, reproductive effector.


OSHA Permissible Exposure Limit (PEL): 5 mg/m3 skin (TWA) (as CN) ACGIH Threshold Limit Value (TLV): 5 mg/m3 (STEL) Ceiling, skin, as CN


This material is expected to be very toxic to aquatic life. This material is expected to be very toxic to terrestrial life.

NFPA Ratings Health: 3 Flammability: 0 Reactivity: 1.

118

TETRA HYDRO FURAN Synonyms Diethylene oxide, oxacyclopentane; THF; tetrahydrofuran

and stabilizer; 1,4-Epoxybutane; Butylene Oxide; Cyclotetramethylene Oxide; Furan, tetrahydro.

Chemical Formula CH2CH2CH2CH2O CAS No. 109-99-9 Molecular Weight 72.11

Emergency Overview Danger! Extremely flammable liquid and vapor. Vapor may cause flash fire. May form explosive peroxides. Harmful if swallowed or inhaled. Causes irritation to skin, eyes and respiratory tract. Affects central nervous system.

Inhalation Causes irritation to the respiratory tract. Symptoms may include coughing, shortness of breath. THF is an anesthetic agent in high concentrations. Overexposure may cause dizziness, headache, nausea and possible fluid in the lungs. May cause liver, kidney or lung injury.

Ingestion Causes irritation to the gastrointestinal tract. Symptoms may include nausea, vomiting and diarrhea. May cause sore throat and abdominal pain. May cause liver or kidney injury.

Skin Contact Causes irritation to skin. Symptoms include redness, itching, and pain. Eye Contact Causes irritation, redness, and pain. Contact may cause permanent eye damage. Chronic Exposure Repeated or high exposures may cause kidney or liver damage; may affect the

lungs. Repeated skin exposure can cause dryness, cracking of skin and rash. Fire Flash point: -14C (7F) CC. Autoignition temperature: 321C (610F).

Flammable limits in air % by volume: lel: 2.0; uel: 11.8 Extremely Flammable Liquid and Vapor! Vapor may cause flash fire. Dangerous fire hazard when exposed to heat or flame.

Explosion Above flash point, vapor-air mixtures are explosive within flammable limits noted above. May form explosive organic peroxides when exposed to air or light or with age. Vapors can flow along surfaces to distant ignition source and flash back. Sealed containers may rupture when heated.

Stability Stable in closed containers with oxygen and light excluded. Distillation or evaporation can concentrate peroxides (if present) to create an explosion hazard.

Conditions To Avoid Heat, flame, ignition sources, incompatibles, light, and air. Hazardous Decomposition Products

Carbon dioxide and carbon monoxide may form when heated to decomposition. May also release toxic and irritating vapors.

Incompatibilities Tetrahydrofuran reacts violently with air on standing. LiAlH2, strong oxidizers, NaAlH2 and potassium hydroxide. Will attack some forms of plastics, rubbers and coatings.

Toxicity Oral rat LD50: 1650 mg/kg. Inhalation rat LC50: 21,000 ppm/3H. Investigated as a tumorigen, mutagen, reproductive effector.


OSHA Permissible Exposure Limit (PEL): 200 ppm (TWA). ACGIH Threshold Limit Value (TLV): 200 ppm (TWA), 250 ppm (STEL)

Environmental Fate When released into the soil, this material is expected to leach into groundwater, this material is expected to quickly evaporate. When released into water, this material may biodegrade to a moderate extent. This material is not expected to significantly bioaccumulate. When released into the air, this material may be removed from the atmosphere to a moderate extent by wet deposition.


96-hour LC50,fathead minnows: 2160 mg/L.


119

TRI ETHYL AMINE

Synonyms Diethylaminoethane; N,N-Diethylethanamine; TEA. Chemical Formula (CH3 CH2)3N CAS No. 121-44-8 Molecular Weight 101

Emergency Overview Danger! Extremely flammable liquid and vapor. Harmful if swallowed, inhaled or absorbed through skin. Corrosive. Causes burns to skin, eyes, and respiratory tract. Affects the cardiovascular system, liver, and kidneys.

Inhalation Corrosive. Toxic by inhalation. Vapors cause irritation to the respiratory tract; symptoms may include sneezing, coughing, nausea, difficulty in breathing, and pulmonary edema.

Ingestion Corrosive. Toxic! May cause burns of the mouth, throat, and stomach with severe abdominal pain and collapse. Aspiration into the lungs may occur during swallowing or vomiting, resulting in lung damage.

Skin Contact Corrosive. Contact can cause redness, pain, and skin burns. Can be absorbed through the skin causing systemic poisoning.

Eye Contact Corrosive. Liquid contact will produce severe eye injury. Vapors are irritating, causing redness, pain, blurred vision, lacrimation, conjunctivitis, and corneal edema. Corneal injury may be severe and extensive, and if not treated promptly, could result in permanent impairment of vision.

Chronic Exposure May cause secondary burns to skin from long exposure. Animal studies have shown target organ effects on heart, liver and kidneys.

Fire Flash point: -9C CC. Autoignition temperature: 249C. Flammable limits in air % by volume: lel: 1.2; uel: 8.0. Extremely Flammable.

Explosion Above flash point, vapor-air mixtures are explosive within flammable limits noted above. Vapors can flow along surfaces to distant ignition source and flash back. Closed containers exposed to heat may explode. Contact with strong oxidizers may cause fire. Sensitive to static discharge.

Stability Stable under ordinary conditions of use and storage. Strongly alkaline; will undergo strong exothermic reaction with acids to form amine salts.

Conditions To Avoid Heat, flame, sources of ignition, light and incompatibles. Hazardous Decomposition Products

Burning may produce carbon monoxide, carbon dioxide, nitrogen oxides.

Incompatibilities Acids, oxidizers, chlorine, hypochlorite, halogenated compounds and nitrogen tetraoxide. N-nitrosamines, many of which are known to be potent carcinogens, may be formed when this product comes in contact with nitrous acid, nitrates or atmospheres with high nitrous oxide concentrations.

Toxicity Oral rat LD50: 460 mg/kg; skin rabbit LD50: 570 ul/kg; inhalation mouse LC50: 6 gm/m3; eye irritation, rabbit,standard Draize: 250 mg open, severe; investigated as a mutagen.


OSHA Permissible Exposure Limit (PEL): 25 ppm(100 mg/m3) (TWA)-ACGIH Threshold Limit Value (TLV): 1 ppm (TWA)skin, 3 ppm (STEL) skin A4, Not classifiable as a human carcinogen.


When released into the soil, this material may leach into groundwater, this material may evaporate to a moderate extent. When released into water, this material may evaporate to a moderate extent. This material has an estimated bioconcentration factor (BCF) of less than 100. This material is not expected to significantly bioaccumulate. When released into the air, this material is expected to be readily degraded by reaction with photochemically produced hydroxyl radicalsthis material is expected to be readily removed from the atmosphere by wet deposition.


Inventys Hazop Final 100 -...

Documents

Transcript of Inventys Hazop Final 100 -...