RISK ASSESSMENT - environmentclearance.nic.inenvironmentclearance.nic.in/writereaddata/FormB/EC/Risk_Assessmen… · 1.2 THE ASSIGNMENT Mr. Subhash Bonde ... Expert – Risk Assessment

RISKASSESSMENT

(QRA)

At

M/S. IDEAL CHEMI PLAST PVT. LTD.PLOT NO. A - 1 & A - 2, MIDC BADLAPUR,

VILLAGE: KULGAON, DIST.: THANE, MAHARASHTRA – 421 503.

MARCH 2017

2

CONTENTSSECTION DESCRIPTION PAGE NO.

1. EXECUTIVE SUMMARY. 03

2. HAZARD IDENTIFICATION. 172.1 Site Overview. 172.2 Process Description. 172.3 List Of Materials. 17

2.3.1 Finished Products. 172.3.2 Raw Materials. 17

2.4 Inventory Analysis. 172.5 Classification Of Hazardous Chemicals. 172.6 MSDS. (Highlights). 182.7 DOW F & E Index. 232.8 MOND Index Assessment. 282.9 Preliminary Hazard Analysis. 40

2.10 HAZOP Study. 42

3. FAILURE FREQUENCY ANALYSIS. 433.1 Event Tree – Flammable Solvent release. 433.2 Event Tree – Flammable Gas release. 44

4. CONSEQUENCE ANALYSIS. 454.1 Introduction. 454.2 Butyl Acrylate release. 464.3 HSD release. 474.4 Methyl Metha Aacrylate release. 484.5 Natural Gas (PNG) release. 494.6 Propionaldehyde release. 514.7 Styrene release. 534.8 Xylene release. 54

5. IMPACT ASSESSMENT (PROBIT). 575.1 Thermal Radiation Impact. 575.2 Over Pressure Impact. 585.3 Toxicity Impact. 59

6. RISK ESTIMATION. 606.1 Individual Risk Isopleths. 606.2 Societal Risk (F – N Curve). 61

7 RISK MITIGATION MEASURES. 62

LIST OF ANNEXURESECTION DESCRIPTION PAGE NO.

1. GLOSSARY. 632. ABBRIVATIONS. 663. REFERENCES. 67

3

SECTION 1: EXECUTIVE SUMMARY

1.1 INTRODUCTION

1.1.1 M/s. Ideal Chemi Plast Pvt. Ltd. is located at Plot No. A1 & A2, MIDC

Badlapur, Village –Kulgaon, dist. Thane , Maharashtra.

1.1.2 The proposed product mix will be as follows;

TABLE NO. 1.1: LIST OF PRODUCTS FOR ENVIRONMENTAL CLEARANCE

SR. NO. PRODUCT EXISTING(MT/M)

ADDITIONPROPOSED

(MT/M)

FINAL(MT/M)

Scale upfactor

1 MF/UF Resins 4.5 0.9 5.4 1.202 Alkyl Resins 12.5 1.9 14.4 1.153 Polyester Resins 12.5 1.9 14.4 1.154 Acrylic Resins 4.4 4.5 8.9 2.02

TOTAL 33.9 9.2 43.1

Quantity of the product may vary individually in each group keeping total quantity ofall groups same.

PRODUCT WISE RAW MATERIALS

Sr. No. Raw Material AminoResins

PolyesterResins

AlkydResins

AcrylicResins

1 Fatty Acids/Fatty oils - - √ -2 Polyols/Glycols/Amines √ √ √ -3 Organic Acids/Anhydride √ √ √ -4 Paraform √ - - -5 Acrylic Monomer(MMA,BA,NBMA etc) - - - √6 Solvents (Xylene, MTO, C-IX, C-X,

BA.BuOH etc.)√ √ √ √

7 Catalysts √ √ √ √8 Water in process (LPD) √ - - -

1.2 THE ASSIGNMENT

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

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

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

Fine Envirotech Engineers, Mumbai this study in compliance of above requirements.

4

1.3 SCOPE OF WORK

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

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

plan.

1.4 METHODOLOGY

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

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

and Forests Government of India.

The major steps are as outlined below;

Hazard Identification. Failure Frequency Analysis. Consequence Analysis. Impact Assessment. Protective System & Hazard Analysis. Risk Mitigation Measures. DMP.

1.5 HAZARD IDENTIFICATION

1.5.1 INVENTORY ANALYSIS

1.5.1.1 HAZARDOUS CHEMICALS

Chemicals stored or handled at site are Hazardous chemicals which

satisfies; any of the following criteria.

5

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

2. Criteria laid down in part I or is listed in Column 2 of Part II Schedule Iappended to “The Maharashtra Factories (Control of Industrial MajorAccident Hazards) Rules, 2003” or

3. Listed in Column 2 of Schedule 2 appended to these rules or4. Listed in Column 2 of “The Second Schedule appended to the Factories

Act, 1948”.5. “The Hazardous Waste (Management and Handling) Rules, 1989”

Amended 2000 and 2003.

1.5.1.2 MSDS

MSDS of Styrene and Xylene are enclosed in Section No. 2 and

MSDS for others are maintained at site.

1.5.1.3 PROPERTIES

PROPERTIES PART ISr.No.

NAME CAS LEL UEL F.P B.P. NFPA HAZARDINDEX

% % 0C 0C Nh Nf Nr

1 Butyl acrylate 141-32-2 1.3 9.9 36 147.3 2 2 22 Butyl cellosolve3 Caustic flakes4 C-X?C9 68477-54-

31 - 45 155- 210 2 2 1

5 di ethylene glycol 111-46-6 1.6 12.2 154 244 1 1 06 Glycerine7 Hydroxy methyl

ethaacrylate8 Hypophosphorus acid9 Melamine 108-78-1

10 Methyl metha acrylate 80-62-6 1.7 12.5 10 100.5 2 3 211 n-butanol 71-36-3 1.4 11.2 37 118 1 3 012 neo pentyn glycol13 Paraformaldehyde 30525-89-4 71 120-180 2 1 014 Phthalic anhydride 85-44-9 1.7 10.4 152 284 2 1 015 Soya fatty acid16 Styrine monomer 100-42-5 1.1 6.1 31 146 2 3 217 Tert. Butyl per benzoate18 Xylene. 1330-20-7 1 7 32 144 2 3 0

6

PROPERTIES PART IISr.No.

NAME CAS TLV STEL IDLH TOXICITYORALLD50

DERMALLD50

INHALLC50

ppm ppm ppm mg/kg. ml/kg. mg/m3

1 Butyl acrylate 141-32-2 22 Butyl cellosolve3 Caustic flakes4 C-X?C9 68477-

54-35

TWA100 >2000 13.3g/kg 1.65 mg/l

5 di ethylene glycol 111-46-6 10TWA

- - 15600 11.89 >10000mg/l

6 Glycerine7 Hydroxy methyl

ethaacrylate8 Hypophosphorus acid9 Melamine 108-78-1 -

10 Methyl metha acrylate 80-62-6 5011 n-butanol 71-36-3 50 790 3400 800012 neo pentyn glycol13 Paraformaldehyde 30525-89-414 Phthalic anhydride 85-44-9 1 - - 1530 >21015 Soya fatty acid16 Styrine monomer 100-42-5 50 42517 Tert. Butyl per benzoate18 Xylene. 1330-20-

7100 150 4300 >1700 5000

1.5.1.4 INVENTORY

SrNo.

Name Maximum Qty Stored (Mt) Mode Of Storage

Existing ProposedAddition

Final Location

1 Paraformaldehyde 8 2 10 25 kg 400 bags Storage B

2 Soya fatty acid 32 -- 32 15 kl 2 tanks Tank no.1 & 2

3 di ethylene glycol 10 - 10 200 kg 50barrels

Storage A

4 neo pentyn glycol 5 - 5 25 kg 125 bags Storage B

5 Glycerine 10 - 10 200 kg 40barrels

Storage A

6 Melamine 5 - 5 25 kg 200 bags Storage B

7 Costic flakes 0.5 - 0.5 25 kg 20 bags Storage B

8 Methyl metha acrylate 10 5 15 200 kg 75barrels

Storage A

9 Butyl acrylate 8 2 10 200 kg 50barrels

Storage A

10 Styrine monomer 10 5 15 200 kg 75barrels

Storage A

11 Hydroxy methyl 6 4 10 200 kg 50barrels

Storage A

7

ethaacrylate

12 Xylene 40 - 40 27 kl 2 tanks Tank no. 3 & $

13 Butyl cellosolve 10 - 10 27 kl 1 tank Tank no.5

14 n-butanol 20 - 20 27 kl 1 tank Tank no.6, underground

15 C-X 20 - 20 27 kl 1 tank Tank no. 7

16 Phthalic anhydride 30 - 30 25 kg 1200bags

Storage B

17 Tert. Butyl per benzoate 1 - 1 20 kg 40 carboy Storage A

18 Hypophosphorus acid 0.8 - 0.8 25 kg 16 carboy Storage A

1.5.1.5 CLASSIFICATION OF HAZARDOUS CHEMICALS

HAZARDOUS CHEMICALS CLASSIFICATION

Sr.No. Group Material Name Maximum Quantity

Stored (Mt)

Threshold Qty.Mt.

for MAH (Sch.2)*

1 5(3) Very Highly FlammableLiquids. Methyl Metha

Acrylate.2 5(4) Highly Flammable

Liquids.MTO. 2500Styrene.Butyl Acrylate.Xylene.

3 5(5) Flammable Liquids. C-9. 5000

1.5.1.6 The inventory of hazardous chemicals is less than the threshold quantity to

qualify as Major Accident Hazards installation (MAH).

1.6 DOW F&E INDEX

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

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

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

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

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

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

Section No. 2.8.

8

DOW F & E INDEX

Sr.No. Storage Installation

DOWF&E

Index

TheDegree Of

Hazard

Radius OfExposure M

DamageFactor

Area OfExposure M2

ToxicityIndex

ToxicityCategory

1 Xylenes 39.2 Light 10.0 0.33 314 3.35 I2 Styrene 54 Light 13.8 0.52 598 4.28 I3 Furnace Oil 17.4 Light 4.5 0.11 63 - -4 C-10 20 Light 5.1 0.10 81 - -5 Methyl Metha

Acrylate55.5 Light 14.0 0.51 615 4.28 I

6 Butyl Acrylate 53.5 Light 13.7 0.51 589 6.28 II7 N butanol 36.6 Light 9.3 0.3 271 4.31 I

1.7 MOND INDEX ASSESSMENT

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

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

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

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

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

MOND INDEX ASSESSMENT

Sr. No. Installation EquivalentDOW Index

Fire Index InternalExplosion Index

AerialExplosion Index

Over AllHazard Rating

1 Xylenes tank 3,4 166 3.81Low

3.6Moderate

11.31Low

953High Group I

2 C-10 62 2.25Low

2.85Moderate

6.36Light

210Moderate

3 Styrene 124 3.6Low

2.5Low

10.47Low

506High Group I

4 Methyl Metha Acrylate 124 3.6Low

2.5Low

10.47Low

506High Group I

5 Butyl Acrylate 121 2.4Low

2.5Low

8.73Light

398Moderate

6 N butanol tank 6 166 3.81Low

3.6Moderate

11.31Low

953High Group I

MOND INDEX ASSESSMENT : MONOMER STORAGE SHED

Sr.No. Index Base Line Study –BeforeExpansion

After Expansion

1 Equivalent dow index 130 1342 Fire index 8.16

Moderate12

High3 Internal explosion index 2.5

Low2.5

Low4 Aerial explosion index 13.53

Low15.27Low

5 Over all hazard rating 815High Group I

1040High Group I

9

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

satisfactory manner by providing adequate off setting measures, giving full

regard to the hazards indicated by the assessment provided adequate depends

heavily upon the maintenance of the hardware and of the management

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

rise.

1.8 COMPATIBILITY/ REACTIVITY HAZARD

TABLE NO. 1.6: COMPATABILITY /REACTIVITY HAZARD MATRIX

Chemicals Mixing With →

But

yl A

cryl

ate

But

yl C

ello

solv

e

Die

thyl

ene

Gly

col

Gly

ceri

ne

Met

hyl

Met

hacr

ylat

e

Sty

rene

1 Butyl Acrylate SR2 Butyl Cellosolve C3 Diethylene Glycol C Y4 Glycerine C Y Y5 Methyl Methacrylate C C C C SR6 Styrene C C C C C SR

CHART LEGEND

Y Compatible - No hazardous reactivity issues expected

N Incompatible - Hazardous reactivity issues expected

C Caution - May be hazardous under certain conditions

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

1.9 HAZOP STUDY(Enclosed separately).

1.9.1 Identification of hazards by HAZOP study is carried out, the thrust area beingthe environmental issues in the proposed activities. The report is “Enclosedseparately”. The methodology adopted is described in the report.

10

1.9.2 HAZOP COMMITTEEHAZOP committee was formed under the chairmanship of the ProjectProponent with members of the project team and Mr. Subhash Bonde asModerator.

1.9.3 BRIEF PROCESS DESCRIPTIONAlkyd, Amino and Polyester ResinsRaw Materials with reflux solvent are charged to reactor. Material iscontinuously stirred under heating to required temperature. Reflux starts afterreaching required temperature, water of reaction is removed and solvent isrecirculated. After desired water removal and desired viscosity is achieved.The products are partially cooled and thinned with solvent to desired solidcontent, after testing the sample batch is discharged in drums or tank with orwithout filtration as required.

Acrylic Resins

Solvent is first charged to the vessel small quantity of monomer mix is alsoadded. The contents are heated till reflux. After getting desired reflux ratemonomer mixture is added at desired constant rate after complete additionproducts are checked for Desired Properties. Finally the material is filtered andfilled in drums. No water of reaction is evolved during the process. No spentsolvents are generated in this process.

1.9.4 UNIT PROCESS AND UNIT OPERATIONS

Unit Process/Operation

AminoResins

PolyesterResin

AlkydResin

AcrylicResin

Remark

Esterification. √ √ √ Byproduct: waterThermalpolymerization √ √ √

Side reaction -Increase in viscosityof material.

Oxidation of rawmaterials √ √ √

Side reaction -Development ofcolour

Decomposition ofinitiator

√ Side reaction

Homogenouspolymerization

√ Side reaction

Blending. √ √ √ √Filtration. √ √ √ √Packing √ √ √ √Mixing √ √ √ √Refluxing √ √ √ √

Reaction Exotherm.Critical To Control Moderate Mild

11

REACTIONS

TYPICAL ESTERIFICATION

FLOW CHART

MATERIAL BALANCE (TYPICAL)

ALKYD RESININPUT OUTPUT

SN Name of Raw Material Kg/Day SN Name of Products Kg/Day1 Fatty Acids/Fatty oils 3269 1 Alkyd Resin 144002 Ployols/Glycols/Amines 2203 2 Evaporation Loss 8.000

3 Organic Acids/Anhydride 3859 3 Effluent (Water ofReaction) 706

4 Solvents (Xylene, MTO,C-IX,C-X, BA. BuOH etc.)

5761

5 Catalysts 22Total 15114 Total 15114

12

POLYESTER RESININPUT OUTPUT

SNName of Raw Material Kg/Day

SNName of Products

Kg/Day1 Ployols/Glycols/Amines 3490 Polyester Resins 144002 Organic Acids/Anhydride 6015 Evaporation Loss 10

3Solvents(Xylene,MTO,C-IX,C-X,BA.BuOH etc.)

5775 Effluent (Water ofReaction) 889


ACRYLIC RESININPUT OUTPUT

Sr.No. Name of Raw Material Kg/Day SN Name ofProducts

Kg/Day

1 AcrylicMonomer(MMA,BA,NBMA etc)

6223 1 Acrylic Resin 8900

2 Solvents(Xylene,MTO,C-IX,C-X,BA.BuOH etc.)

2660 2 EvaporationLoss

107


AMINO RESININPUT OUTPUT

SN Name of Raw Material Kg/Day SN Name of ProductsKg/Day

1 Paraform 1519 1 AminoResins(MF/UfResins)

5400

2 Ployols/Glycols/Amines 1360 2 Evaporation Loss 1613 Organic Acids/Anhydride 20 3 Gas Emission 54 Solvents(Xylene,MTO,C-IX,

C-X,BA.BuOH etc.)3695 4 Process Sludge 10

5 Catalysts 38 5 Effluent (Water ofReaction)

1269

6 Water in process 213Total 6845 Total 6845

13

1.9. 7 NODES

The HAZOP Study carried out under following NODES;

NODES FOR HAZOP STUDY

NODE 1 Tank Farm.

NODE 2 Process operations

NODE 3 ETP

NODE 4 All other unit processes and operations.

1.9.8 MODES

Mode of operation is batch wise.

1.9.9 IDENTIFICATION OF HAZARDS

1.9.9.1 HAZARD RATING

Probability of each hazard according to its likelihood of

occurrence and the severity of each hazard according to its

potential for harm was estimated on 1 to 5 scale. By

multiplying these two factors i.e. probability and severity, a

range of risk ratings between 1 to 25 is obtained.

1.9.9.2 Identified hazards/ events having risk rating in 16 to 25 range

summerised as follows;

STORAGE AND HANDLING: Fire/ explosion hazard at tank farm.

Reactivity/ compatibility hazards due to large number

of chemicals.

PROCESS OPERATIONS: Fire/ Explosion hazard at reactor due to uncontrolled

exothermic reactions.

Health hazard due to vapors emissions at work place.

Fire explosion hazard due to static charge as source

of ignition in handling of solvents.

Toxic/ flammable gas/vapors release at vent.

14

1.9.9.3 Following accident scenario is considered forConsequence Analysis. Spill of flammable solvent followed by pool fire.

Release of toxic gas.

Release of flammable gas.

1.10 CONSEQUENCE ANALYSIS

1.10.1 The potential consequences from the hazardous scenarios identified are

determined and the impact zones modeled using ALOHA and PHAST

software tools. The primary consequence types are pressure wave, thermal

radiations and toxic gas release. The neutral atmospheric stability conditions

and ambient temperature of 30 oC, wind speed was 4.0 m/s. and humidity

(50%) used for Consequence Analysis.

1.10.2 RESULTS

CONSEQUENCE ANALYSIS RESULTS

Downwind Affect Distance (m)

Sr.No.

Accident

Scenario

Toxic Vapor Cloud

Flammable

Vapor Cloud

LEL

Blast Over

Pressure psi

Thermal

Radiation

(KW/m2)

ERPG

3

ERPG

2

ERPG

1IDLH 60 % 10 % 8 3.5 1 10 5 2

1 Butyl

Acrylate.

<10 19 492 <10 <10 <10 - - - <10 <10 <10

2 HSD. - - - - - - - - - 11 12 13.5

3 Methyl

Metha

Acrylate.

<10 24 66 <10 <10 <10 <10 <10 <10

4 Styrene. <10 <10 14 <10 <10 <10 - - - <10 <10 <10

5 Xylene. - - - <10 <10 <10 - - - <10 <10 <10

15

DISPERSION DISPERSION POOL FIRE

BUTYL ACRYLATE MONO METHYL ACRYLATE METHYL METHAACRYLATE

1.11 FREQUENCY ASSESSMENT1.11.1 Event trees begin with an initiating event and work toward a final result. This

approach is inductive. The method provides information on how a failure canoccur and the probability of occurrence.

1.11.2 Frequency of the incident is estimated by Event Tree.

S.N. EVENT EVENT FREQUENCY/ YR

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

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

1.12 IMPACT ASSESSMENT

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

1.12.2 RESULTSPROBIT CORRELATION RESULTS

EventLevel ofconcern

Affectdistance

Impact Probit correlationFatality

%

Diesel 10.0KW/m2

11 m ThermalRadiations.

Pr = –14.9+ 2.56 ln [(t×I4/3)] 0

Xylene. 10.0KW/m2

< 10 m ThermalRadiations.

Pr = –14.9+ 2.56 ln [(t×I4/3)] 0

* Assuming escape time from fire to safe place exceeds 90 seconds.

16

1.13 RISK ESTIMATION

1.13.1 VULNERABLE ZONE

Contour No. Chemical Color Code Level Of Concern Impact1 Monomers. DOW Damage Radius. 51-54 % Damage.2 N butanol DOW Damage Radius. 30-33 % Damage.3 Solvent Xylene DOW Damage Radius. 30-33 % Damage.4 C X Dow damage radius 10- 11 % Damage5 Furnace oil Dow damage radius 10- 11 % Damage

1.13.2 INDIVIDUAL RISKINDIVIDUAL FATALITY CRITERIA

INDIVIDUAL FATALITY INDIVIDUAL FATALITY CRITERIA1 × 10-4 per yr This contour remains on-site.1 × 10-5 per yr This contour extends into industrial developments only.1 × 10-6 per yr This contour extends into commercial and industrial

developments only.INDIVIDUAL FATALITY QRA RESULTS.

Individual Fatality(IR)

Downwind AffectDistance (M) Remarks

1 × 10-4 per yr <10 This contour remains on-site.1 × 10-5 per yr <10 This contour extends in to notified

industrial area only.1 × 10-6 per yr <10 This contour extends in to notified

industrial area only.A broadly acceptable level of individual risk as per the ALARP (As low as reasonably practicable) concept ofHSE, UK is 10-6/ year.

17

1.13.3 SITE SURROUNDING : MIDC NOTIFIED AREA

1.13.4 SITE SURROUNDINGS

18

1.13.5 SOCIETAL RISK

Sr.No.

Event Event FrequencyPer Year

No. OfFatality

CumulativeFrequency

1. Hydrogen Gas Fire/Explosion.

4.4 10-4 1 4.4 10-4

2. Solvent Tank Pool Fire. 1.52 10-3 0 1.96 10-3

The population within the specified radius of vulnerable zone is mainly industrial.

The site surroundings population data analysed. The effects of the proposed site activity are wellcontained within the notified industrial area and indicates within acceptable societal risk.

1.14 FIRE LOAD & FIRE WATER REQUIREMENT

SR.

NO.

NAME CALORIFIC VALUE SR.

NO.

NAME CALORIFIC VALUE

1 Wood. 17-20 MJ/Kg 10 N butanol 14.3 x 10 3 BTU/Lb

2 Paper Average. 16.3 MJ/Kg 11 C-X. 18.0 x 10 3 BTU/Lb

3 Chair (PU Foam). 27 MJ/Kg 12 Formaldehyde 8 x 10 3 BTU/Lb

4 Plastic average. 22.1 MJ/Kg 13 Diesel. 18.7 x 10 3 BTU/Lb

5 Polycarbonate. 28-30 MJ/Kg 14 Xylene 17.6 x 10 3 BTU/Lb

6 ABS Plastic. 34-40 MJ/Kg 15 Styrene. 17.4 x 10 3 BTU/Lb

7 Rubber. 39.5 MJ/Kg 16 Butyl Acrylate. 14.2 x 10 3 BTU/Lb

8 Electrical & Others.* 15 MJ/Kg 17 Methyl Metha Acrylate. 11.9 x 10 3 BTU/Lb

9 Teflon. 5 MJ/Kg

Reference:(1) Fire Protection Manual of TAC: 1982 - 9th Edition.(2) OSID: STD - 116 amended edition – October, 2002.(3) The Maharashtra Fire Prevention and Life Safety Measures Act, 2006 (4) NFPA 557.

19

Installation Description Size Area Factor Area ForFire Load

WaterRating

WaterFlow

RatedTime

Fire WaterRequirement

M m2 m2 lpm/m2 m3/hr hr. m3

TANKFARM

Explosive area 10x8.4 84.0Monomerstorage G+0.5

12.5x8 150.0

FO tank farm 4x2 8.0242.0 0.5 121.0 5 36.3 2 72.6

STORE Open shedstorage G+1

10x 13.7 274.0

Soya fatty acidtank

4.5x2.5 11.3

Butyl cellosolve& C X

2.9x17 49.3

Storage tank 5x2 10.0Storage tank 2.55x2.3 5.8

350.4 0.5 175.2 5 52.6 1 52.6PLANT Plant G+1 10.36x10.34 107.1

Plant G+1 19.65x13.5 265.3Lab R&D 6x2.65 15.9Lab 4.97x3.6 17.8DG 1.5x13.7 2.6

408.7 0.1 40.8 1 2.5 1 2.5Utility Thermopack

G +0.59x3 27.0

Boiler shed 6.7x5.6 37.5Cooling tower 3.5x4.4 1.4Cooling tower 1.5x 1.5 2.3

68.2 0.1 6.8 1 0.4 1 0.4OTHERS ETP 2.4x3.4 8.2

Office 8x3.6 28.8Engg store 5.5x4 22.0

59.0 0.1 5.9 1 0.4 1 0.4TOTAL 128.5 m3

1.15 RISK MITIGATION MEASURES

Following risk mitigation measures are suggested1. Fire hydrant system.

2. Dedicated Fire water storage

3. Consider "Compatibility & Reactivity Hazards" at storage of chemicals.

4. Ensure to collect the organic contaminated fire water generated during fire

fighting operation for decontamination before disposal.

5. A separate document “DMP” based on MCLS Analysis for the site is

developed specifying important locations as follows;

20

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

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

frame.

21

SECTION 2: HAZARD IDENTIFICATION

2.1 SITE OVERVIEW

2.1.1 M/s. Ideal Chemi Plast Pvt. Ltd. is located at Plot No. A1 & A2, MIDC

Badlapur, Village –Kulgaon, dist. Thane , Maharashtra.

2.1.2 Products for Environmental Clearance.

Refer Table No. 1.1 in Section No. 1.

2.2 PROCESS DESCRIPTION

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

equipment details.

2.3 LIST OF MATERIALS

2.3.1 FINISHED PRODUCTS


2.3.2 RAW MATERIALS


2.4 INVENTORY ANALYSIS

HAZARDOUS CHEMICALS

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

the following criteria.

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

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

3. Listed in Column 2 of Schedule 2 appended to these rules OR4. Listed in Column 2 of “The Second Schedule appended to the Factories Act, 1948”.5. “The Hazardous Waste (Management and Handling) Rules, 1989” Amended 2000 and 2003.Properties of the chemicals are checked to classify the hazardous chemicals.


2.5 CLASSIFICATION OF HAZARDOUS CHEMICALS


22

2.6 MSDS

23

24

2.7 DOW F & E INDEX

HAZARDS IDENTIFICATION BY USE OF DOW INDEX:

By Dow's Fire and Explosion Index Method:

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

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

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

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

initiation or escalation of an incident.

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

in realistic terms.

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

The quantitative methodology relies on the analysis based on historical loss

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

loss prevention measures are already taken.

F & EI = MF F3

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

= F1 × F 2

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

Deviation of MF

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

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

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

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

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

Flammability can be determined.

25

General Process Hazard (F1)

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

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

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

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

accessibility and facilities to drainage and spill control.

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

occurrence of a loss accident.

Evaluation of F & EI

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

per the criteria given below:

TABLE NO. 2.5: F&EI RANGE & DEGREE OF HAZARD

F & EI Range Degree of Hazard

0 – 60. Light.

61 – 96. Moderate.

97 – 127. Intermediate.

128 – 158. Heavy.

159 – and above. Severe.

26

DOW FIRE & EXPLOSION INDEX WORKSHEET

PLANT: MONOMER TANK FARM.MATERIALS AND PROCESS: BUTYL ACRYLATE.MATERIAL FACTOR: 24

PENALTY FACTORRANGE

PENALTY FACTORUSED

1. GENERAL PROCESS HAZARDS.Base Factor. 1.0 1.0

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

General Process Hazards Factor (F1). 1.25

2. SPECIAL PROCESS HAZARDS.Base Factor. 1.0 1.0

A. Toxic Materials. 0.20 to 0.80 0.4B. Sub – Atmospheric Pressure. 0.50 00C. Operation in or Near Flammable Range Inerted. – –

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

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

10 mt , Hc 14.2 103 BTU/Lb.– –

1. Liquid or Gases in Process. – –2. Liquid or gases in Storage. – 0.183. Combustible Solids in Storage. – –

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

Special Process Hazards Factor (F2) 1.78

Unit Hazards Factor (F1 F2 = F3). 2.23Fire and Explosion Index (F3 MF) (F & IE). 53.5THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 13.7 meterDAMAGE FACTOR. 0.51AREA OF EXPOSURE. 589 m2

T = [125 +125 × (1 +1.25 + 1.78)]/100 = 6.28 T Category II.

27


PLANT: MONOMER TANK FARM.MATERIALS AND PROCESS: METHYL METHACRYLATE.MATERIAL FACTOR: 24

PENALTY FACTORRANGE

PENALTY FACTORUSED








15 mt , Hc 11.9 103 BTU/Lb.– –





T = [125 + 75 × (1 + 1.25 + 1.8)]/100 = 4.28 T Category I.

28


PLANT: TANK FARM.MATERIALS AND PROCESS: N ButanolMATERIAL FACTOR: 16

PENALTY FACTORRANGE

PENALTY FACTORUSED








20 mt, Hc 14.3 103 BTU/Lb.– –





T = [125 + 75 × (1 + 1.25 + 1.83)]/100 = 4.31 T Category I.

29


PLANT: TANK FARM.MATERIALS AND PROCESS: STYRENE.MATERIAL FACTOR: 24

PENALTY FACTORRANGE

PENALTY FACTORUSED








15 mt , Hc 17.4 103 BTU/Lb.– –




Unit Hazards Factor (F1 F2 = F3). 2.25Fire and Explosion Index (F3 MF) (F & IE). 54THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 13.8 meterDAMAGE FACTOR. 0.52AREA OF EXPOSURE. 598 m2

T = [125 + 75 × (1 + 1.25 + 1.8)]/100 = 4.28 T Category I.

30


PLANT: TANK FARM.MATERIALS AND PROCESS: XYLENE.MATERIAL FACTOR: 16

PENALTY FACTORRANGE

PENALTY FACTORUSED








40 mt, Hc 17.6 103 BTU/Lb.– –




Unit Hazards Factor (F1 F2 = F3). 2.45Fire and Explosion Index (F3 MF) (F & IE). 39.2THE DEGREE OF HAZARD. LIGHTRADIUS OF EXPOSURE. 10 meterDAMAGE FACTOR. 0.33AREA OF EXPOSURE. 314 m2

T = [125 + 50 × (1 + 1.25 +1.96 )]/100 = 3.35 T Category I.

31


PLANT: TANK FARM.MATERIALS AND PROCESS: C-X.MATERIAL FACTOR: 10

PENALTY FACTORRANGE

PENALTY FACTORUSED

1. GENERAL PROCESS HAZARDSBase Factor. 1.0 1.0

A. Exothermic Chemical Reactions. 0.30 to 1.25 0.0B. Endothermic Process. 0.20 to 0.40 0.0C. Material Handling & Transfer. 0.25 to 1.05 0.2D. Enclosed or Indoor Process Unit. 0.25 to 0.90 0.0E. Access. 0.20 to 0.35 0.0F. Drainage and Spill Control. 0.25 to 0.50 0.0


2. SPECIAL PROCESS HAZARDSBase Factor. 1.0 1.0

A. Toxic Materials. 0.20 to 0.80 0.2B. Sub – Atmospheric Pressure. 0.50 0.0C. Operation in or Near Flammable Range Inerted. – –

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

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

20 mt, Hc = 18.7 103 BTU/Lb.– –


H. Corrosion and Erosion. 0.10 to 0.75 0.1I. Leakage – Joint and packing. 0.10 to 1.50 0.1J. Use of fired heaters. – 0.0K. Hot Oil Heat Exchange system > 210 ft. 0.15 to 1.15 0.0L. Rotating Equipment. 0.5 0.0


Unit Hazards Factor (F1 F2 = F3). 2.0

Fire and Explosion Index (F3 MF) (F & IE). 20

THE DEGREE OF HAZARD LIGHT.

RADIUS OF EXPOSURE 5.1 meter.

DAMAGE FACTOR 0.1

AREA OF EXPOSURE 81 m2

32

2.8 MOND INDEX ASSESSMENT

2.8.1 METHODOLOGY

The MOND Index is a rapid hazard

assessment method for use on

chemical plant or in plant design. The

use of this technique puts the hazard

of a plant on a numerical scale, where

form the comparative pictures of all

subdivisions of the plant emerges.

(For details refer MOND INDEX

Manual 1993). The plant installations

having significant inventory of

flammable/ combustible materials

are considered and plant is sub

divided accordingly. MOND INDEX

ASSESSMENT (without offsetting) for

these installations is summerised in

Table No. 1.5.FIGURE NO. 2.1:

THE MOND INDEX PROCEDURE.

FIRE INDEX (F):

The Index concentrates on the amount of flammable material in the unit, its energy

release potential and the area of the unit. The expression is;

N

KBF

And descriptive categories can be derived from the table below.

TABLE NO. 2.1: FIRE INDEX CATEGORY

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

> 250 Very Extreme.

33

EXPLOSION INDICES (E):

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

internal explosion an aerial (vapor cloud) explosion.

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

1001

SPME

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

descriptive categories are given below.

TABLE NO. 2.2: INTERNAL EXPLOSION INDEX CATEGORY

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

AERIAL EXPLOSION INDEX (A):

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

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

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

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

material factor, characteristic of the material.

ptQHEm

BA

1

300

273

10001001

Corresponding descriptive categories are given below;

TABLE NO. 2.3: AERIAL EXPLOSION INDEX CATEGORY

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

34

OVERALL HAZARD RATING (R):

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

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

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

AFEDR 2.01

TABLE NO. 2.4: OVERALL HAZARD RATING CATEGORY

OVERALL HAZARD RATING CATEGORY0 – 20 Mild.

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

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

EQUIVALENT DOW INDEX:

1001

1001

1001

TLQSPMBD

2.8.2 SUB – DIVISION OF PLANT IN UNITS

1. Tank farm.

2. Process plant.

3. Utility.

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

2.9 PRELIMINARY HAZARD ANALYSIS

SR.NO.

ACCIDENT SCENARIO CAUSES CONSEQUENCE ZONE

1. Minor Spill. Hose failure,

Pipe line/ pump gland leakage,

Gasket failure,

Spill of acidic/ alkaline/ flammable

material.

Local.

2. Large Spill. Failure of bottom valve or

catastrophic failure of reactor/

storage tanks.

Overturning of tanker.

Off Site Potential.

3. Fire./explosion Polymerization,

Flammable solvent fire/explosion

Off Site Potential.

4. Release of toxic gas. Hydrogen chloride at vent. Off Site Potential.

5. Electric Fire. At electrical installations,

Transformer area,

Loose cable,

Overloading on cables etc.

Local.

6. Fall of Structure. Earthquake, poor maintenance. Local.

7. Air, Water, Soil

Pollution.

Leak of spill of any material – Solid,

Liquid or Gaseous.

Off Site Potential.

8. Heavy rain fall/

Flooding.

Natural calamity. Off Site Potential.

9. Risks from surrounding

company.

Due to leak of toxic gas from the

process/ storage tank/ cylinders etc.

Explosion in reactor or tank due to

overpressure.

Due to unsafe material handling,

loading – unloading and failure in

process control.

Off Site Potential.

57

HAZOP STUDY

At

M/S. IDEAL CHEMI PLAST PVT. LTD.PLOT NO. A - 1 & A - 2, MIDC BADLAPUR,

VILLAGE: KULGAON, DIST.: THANE, MAHARASHTRA – 421 503.

MARCH 2017

58

CONTENTS

SECTION DESCRIPTIONPAGE

NO.

2.9.1 HAZOP Methodology.

2.9.2 Introduction

2.9.3 Compatibility/ Reactivity Hazards

2.9.4 HAZOP Worksheets

NODE 1: Tank farm

Sub node 1.1 : Xylene storage tank

Sub node 1.2 : Monomer storage

Sub node 1.3 : Monomer storage

NODE 2: Esterification

NODE 3: ETP.

NODE 4: Other Unit Processes and Unit Operations

59

2.10.1 HAZOP METHODOLOGYHAZOP

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

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

now used to great satisfaction throughout the chemical industries.

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

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

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

final design phase and during modifications of the existing plants.

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

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

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

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

consequences.

DATA COLLECTION

60

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

HAZOP COMMITTEE

The HAZOP committee is formed as per following guidelines

CHAIRMAN OCCUPIER / FACTORY MANAGER.

CO –ORDINATOR Safety officer.

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

PROJECT or DESIGNENGINEER For a new design

MAINTENANCE MANAGERFor operating plant

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

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

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

INSTRUMENT /DESIGNENGINEER

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

RESEARCH CHEMIST If new chemistry is involved.

STUDY PROCEDURE

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

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

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

opposites all conceivable eventualities.

61

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

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

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

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

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

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

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

analysis is also carried out.

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

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

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

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

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

members have the necessary background knowledge of the process.

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

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

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

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

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

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

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

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

MEANING OF THE GUIDE WORDS

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

letters):

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

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

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

vapor, solids.

62

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

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

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

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

assessment.

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

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

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

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

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

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

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

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

recommended considering the probability and seriousness of the hazard Recommendations

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

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

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

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

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

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

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

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

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

enough etc.)

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

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

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

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

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

occasionally or every probable).

63

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

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

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

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

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

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

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

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

should again be recorded for attention outside the meeting.

DOCUMENTATION

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

details:

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

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

P & IREFERENCE

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

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

DESIGNINTENTION

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

UNIT/EQUIPMENT

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

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

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

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

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

64

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

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

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

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

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

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

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

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

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

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

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

copies were used for the “HAZOP” Study.

65

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

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

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

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

Which segment of process or procedure were reviewed?

Which guide words & parameters were considered?

The cause and consequences of each deviation studied.

Whether a potential problem exists?

What are the existing safeguards?

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

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

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

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

documented as “HAZOP WORKSHEET”.

STUDY RESULTS/ FINDINGS

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

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

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

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

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

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

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

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

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

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

recorded.

HAZARD RATING METHODOLOGY

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

66

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

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

HAZARD PROBABILITY & SEVERITY RATING.

Hazard Probability Value Hazard Severity Value

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

HAZARD RATING

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

1 and 25 is obtained.

HAZARD RATING MATRIX.

SEVERITY

PR

OB

AB

ILIT

Y

Very High(5)

High.(4)

Moderate(3)

Slight(2)

Nil.(1)

Very Likely. (5) 25 20 15 10 05

Likely. (4) 20 16 12 08 04

Quite Possible. (3) 15 12 09 06 03

Possible. (2) 10 08 06 04 02

Not Likely. (1) 05 04 03 02 01

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

following.

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

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

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

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

likely to have the greatest impact.

67

2.10.2 INTRODUCTION

1 M/s. Ideal Chemi Plast Pvt. Ltd. is located at Plot No. A1 & A2, MIDC Badlapur,

Village –Kulgaon, dist. Thane , Maharashtra.

2 The proposed product mix will be as follows;

TABLE NO. 1.1: LIST OF PRODUCTS

SR. NO. PRODUCT EXISTING(MT/M)

ADDITIONPROPOSED

(MT/M)

FINAL(MT/M)

Scale upfactor

1 MF/UF Resins 4.5 0.9 5.4 1.202 Alkyl Resins 12.5 1.9 14.4 1.153 Polyester Resins 12.5 1.9 14.4 1.154 Acrylic Resins 4.4 4.5 8.9 2.02

TOTAL 33.9 9.2 43.1

.3 The present report is part of the QRA report for the proposed manufacturing facility

and prepared towards compliance to the requirements for environmental clearance.

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

environmental issues in the proposed activities. The methodology adopted is above...

5 HAZOP COMMITTEE

HAZOP committee was formed under the chairman ship of Project Proponent with

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

6 PRODUCT WISE RAW MATERIALS

Sr. No. Raw Material AminoResins

PolyesterResins

AlkydResins

AcrylicResins

1 Fatty Acids/Fatty oils - - √ -2 Polyols/Glycols/Amines √ √ √ -3 Organic Acids/Anhydride √ √ √ -4 Paraform √ - - -5 Acrylic Monomer(MMA,BA,NBMA

etc)- - - √

6 Solvents (Xylene, MTO, C-IX, C-X,BA.BuOH etc.)

√ √ √ √

7 Catalysts √ √ √ √8 Water in process (LPD) √ - - -

68

7 IMPORTANT SAFETY PROPERTIES

PROPERTIES PART ISr.No.

NAME CAS LEL UEL F.P B.P. NFPA HAZARD INDEX

% % 0C 0C Nh Nf Nr

1 Butyl acrylate 141-32-2 1.3 9.9 36 147.3 2 2 22 Butyl cellosolve3 Caustic flakes4 C-X?C9 68477-54-3 1 - 45 155- 210 2 2 15 di ethylene glycol 111-46-6 1.6 12.2 154 244 1 1 06 Glycerine7 Hydroxy methyl ethaacrylate8 Hypophosphorus acid9 Melamine 108-78-1

10 Methyl metha acrylate 80-62-6 1.7 12.5 10 100.5 2 3 211 n-butanol 71-36-3 1.4 11.2 37 118 1 3 012 neo pentyn glycol13 Paraformaldehyde 30525-89-4 71 120-180 2 1 014 Phthalic anhydride 85-44-9 1.7 10.4 152 284 2 1 015 Soya fatty acid16 Styrine monomer 100-42-5 1.1 6.1 31 146 2 3 217 Tert. Butyl per benzoate18 Xylene. 1330-20-7 1 7 32 144 2 3 0

PROPERTIES PART IISr.No.

NAME CAS TLV STEL IDLH TOXICITYORALLD50

DER LD50 INHALLC50

ppm ppm ppm mg/kg. ml/kg. mg/m3

1 Butyl acrylate 141-32-2 22 Butyl cellosolve3 Caustic flakes4 C-X?C9 68477-

54-35

TWA100 >2000 13.3g/kg 1.65 mg/l

5 di ethylene glycol 111-46-6 10TWA

- - 15600 11.89 >10000mg/l

6 Glycerine7 Hydroxy methyl

ethaacrylate8 Hypophosphorus acid9 Melamine 108-78-1 -

10 Methyl metha acrylate 80-62-6 5011 n-butanol 71-36-3 50 790 3400 800012 neo pentyn glycol13 Paraformaldehyde 30525-

89-414 Phthalic anhydride 85-44-9 1 - - 1530 >21015 Soya fatty acid16 Styrine monomer 100-42-5 50 42517 Tert. Butyl per

benzoate18 Xylene. 1330-20-

7100 150 4300 >1700 5000

69

8 PRODUCT WISE UNIT PROCESSES & OPERATIONS

Unit processes and operations involving or likely to involve one or more hazardous chemicals aslisted under SCHEDULE – 4 [See Rule 2(c), 2(e)] “The Manufacture Storage Import HazardousChemical Rules, 1989”.

Unit Process/Operation

AminoResins

PolyesterResin

AlkydResin

AcrylicResin

Remark

Esterification. √ √ √ Byproduct: waterThermalpolymerization √ √ √

Side reaction -Increase in viscosityof material.

Oxidation of rawmaterials √ √ √

Side reaction -Development ofcolour

Decomposition ofinitiator

√ Side reaction

Homogenouspolymerization

√ Side reaction

Blending. √ √ √ √Filtration. √ √ √ √Packing √ √ √ √Mixing √ √ √ √Refluxing √ √ √ √

Reaction Exotherm.Critical To Control Moderate Mild

9 BRIEF PROCESS DESCRIPTION

ALKYD, AMINO AND POLYESTER RESINS

Raw Materials with reflux solvent are charged to reactor. Material is continuously

stirred under heating to required temperature. Reflux starts after reaching required

temperature, water of reaction is removed and solvent is recirculated. After desired

water removal and desired viscosity is achieved. The products are partially cooled

and thinned with solvent to desired solid content, after testing the sample batch is

discharged in drums or tank with or without filtration as required.

ACRYLIC RESINS

Solvent is first charged to the vessel small quantity of monomer mix is also added.

The contents are heated till reflux. After getting desired reflux rate monomer mixture

70

is added at desired constant rate after complete addition products are checked for

Desired Properties. Finally the material is filtered and filled in drums. No water of

reaction is evolved during the process. No spent solvents are generated in this process.

10 FLOW CHART

11. MAIN REACTIONS

Condenser

Receiver

Water of reactionstorage drum

Raw Materials

Monomer Tank

Reactionvessel

Stirred at45-50rpm

Blender /Dilution Tank

Filter

To Drum Fillingor Storage Tank

71

12 MATERIAL BALANCE (TYPICAL)

ALKYD RESININPUT OUTPUT

SN Name of Raw Material Kg/Day SN Name ofProducts

Kg/Day

1 Fatty Acids/Fatty oils 3269 1 Alkyd Resin 14400

2Ployols/Glycols/Amines

22032 Evaporation

Loss 8.000

3Organic Acids/Anhydride

38593 Effluent (Water

of Reaction) 706

4Solvents (Xylene, MTO,C-IX,C-X, BA. BuOH etc.)

5761


POLYESTER RESININPUT OUTPUT

SNName of Raw Material Kg/Day

SNName ofProducts

Kg/Day

1 Ployols/Glycols/Amines 3490 Polyester Resins 14400

2Organic Acids/Anhydride 6015 Evaporation

Loss 10

3Solvents(Xylene,MTO,C-IX,C-X,BA.BuOH etc.)

5775 Effluent (Waterof Reaction) 889


ACRYLIC RESININPUT OUTPUT

Sr.No. Name of Raw Material Kg/Day SN Name of Products Kg/Day1 Acrylic

Monomer(MMA,BA,NBMAetc)

6223 1 Acrylic Resin 8900

2 Solvents(Xylene,MTO,C-IX,C-X,BA.BuOH etc.)

2660 2 Evaporation Loss 107


72

AMINO RESININPUT OUTPUT

SN Name of Raw Material Kg/Day SN Name of Products Kg/Day1 Paraform 1519 1 Amino

Resins(MF/UfResins)

5400

2 Ployols/Glycols/Amines 1360 2 Evaporation Loss 1613 Organic Acids/Anhydride 20 3 Gas Emission 54 Solvents(Xylene,MTO,C-IX,C-

X,BA.BuOH etc.)3695 4 Process Sludge 10

5 Catalysts 38 5 Effluent (Waterof Reaction)

1269

6 Water in process 213Total 6845 Total 6845

13 NODES

The HAZOP study carried out under following nodes;

NODE 1 Tank Farm

NODE 2 Esterification

NODE 3 ETP.

NODE 4 Other Unit Processes & Unit Operations.

14 MODES

Mode of operation is batch wise.

15 HAZOP WORKSHEET

HAZOP worksheets are enclosed under respective NODE in the following sections.

16 HAZARDOUS EVENTS

In conclusion out of all the identified hazards/ events having risk rating in 16 to 25range considered as MCA (Maximum Credible Accident having risk rating 20 to 25range). These events are summarized (repetition excluded) as follows:

STORAGE AND HANDLING

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

73

PROCESS OPERATIONS

Fire/ Explosion hazard at reactor due to uncontrolled exothermic reactions. Health hazard due to vapors emissions at work place. Fire explosion hazard due to Static charge as source of ignition in handling of

solvents. Toxic gas release at scrubber vent.

MCA (MAXIMUM CREDIBLE ACCIDENT) FOR CONSEQUENCE ANALYSIS Spill of flammable solvent followed by pool fire. Release of toxic gas. Release of flammable gas.

1.17 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 timeframe.

74

2.10.3 COMPATABILITY/ REACTIVITY HAZARDS(in case of unintended mix up of chemicals).

PREDICTED HAZARDS REPORT--------------------------------------------------Chemicals and Reactive Groups in this Mixture:BUTYL ACRYLATEBUTYL CELLOSOLVEDIETHYLENE GLYCOLGLYCERINEMETHYL METHACRYLATE MONOMERSTYRENE MONOMER, STABILIZED

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

BUTYL ACRYLATE mixed with itself -INTRINSIC REACTIVE HAZARDS:Potentially self-reactive. See referenced documentation provided in the Chemical ReactivityWorksheet.--- END OF HAZARDS FOR THIS ITEM ---

BUTYL CELLOSOLVE mixed with BUTYL ACRYLATE -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

DIETHYLENE GLYCOL mixed with BUTYL ACRYLATE -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

DIETHYLENE GLYCOL mixed with BUTYL CELLOSOLVE -PREDICTED HAZARDS:No known hazardous reactionPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

75

GLYCERINE mixed with BUTYL ACRYLATE -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

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

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

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

METHYL METHACRYLATE MONOMER mixed with BUTYL ACRYLATE -PREDICTED HAZARDS:May be hazardous but unknownPolymerization reaction may become intense and may cause pressurizationPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

METHYL METHACRYLATE MONOMER mixed with BUTYL CELLOSOLVE -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

METHYL METHACRYLATE MONOMER mixed with DIETHYLENE GLYCOL -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

METHYL METHACRYLATE MONOMER mixed with GLYCERINE -

76

PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

METHYL METHACRYLATE MONOMER mixed with itself -INTRINSIC REACTIVE HAZARDS:Potentially self-reactive. See referenced documentation provided in the Chemical ReactivityWorksheet.--- END OF HAZARDS FOR THIS ITEM ---

STYRENE MONOMER, STABILIZED mixed with BUTYL ACRYLATE -PREDICTED HAZARDS:May be hazardous but unknownPolymerization reaction may become intense and may cause pressurizationPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

STYRENE MONOMER, STABILIZED mixed with BUTYL CELLOSOLVE -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

STYRENE MONOMER, STABILIZED mixed with DIETHYLENE GLYCOL -PREDICTED HAZARDS:May be hazardous but unknownPOTENTIAL GASES:No gases predicted.--- END OF HAZARDS FOR THIS MIXTURE PAIR ---

IDEAL CHEMI PLAST PVT. LIMITED.Plot No. A1 & A2, MIDC Badlapur, Village: Kulgaon, Dist.: Thane, Maharashtra.

NODE 1 OF 4: PROCESS OPERATIONS

77

2.10.4 HAZOP WORK SHEET

NODE – 1 of 4 : Tank farmDESIGN INTENT : Monomer storage tanks - styrene ,Guideword

Parameter Deviation Cause ConsequenceProtectionmeasures

S P R Action suggested

None Flow No flow

while

transfer to

plant

Line blockage Delayed

operation

Supervision 4 3 12 All pipes used to transfer styrene should be

sloped so they can be conveniently drained.

Low spots should be avoided as styrene

may polymerize. If low spots are present,

they should be equipped with taps so

residual styrene can be drained.

Pumps should be designed for easy draining

of any residual styrene.

More Flow More flow

in tank vent

Polymerization Pressurization Supervision 4 3 12

Less Flow Less flow in

tank vent

Vent

blockages

Pressurization Supervision 4 3 12 Tank openings such as vents, arrester

plates, and manways should be inspected

periodically (about every six months) for

polymer buildup.



78




Reverse Flow Moisture Reverse flow at ventduring pumping out

Unsafecondition

Supervision 3 3 9

As wellas

Flow Impurities In supply Unsafecontition

QC tests 3 3 9

Otherthan

Flow Flow ofunintendedmaterial

In error wrong valveoperation

Mix upUnsafecondition

SupervisionDedicated piping

4 2 8

Other Staticcharge

Static chargeaccumulationto dangerouslevel

Static electricityoften accumulateson equipmentused for storageand movements ofStyrene.

Fire/ explosionhazard.

Eaquipments areearthed

4 4 16 When transferring styreneinto a tank, submergedfilling should be used todissipate static electricity.

More Temperature Styrenepolymerizesslowly atroomtemperatureand morerapidly atelevatedtemperatures.

Polymer may formdue to any of thefollowing:High.temperaturesAcids.Peroxides.Oxidizers.Other.

Uncontrolledpolymerizationof Styrene canlead tohardening andplugging ofequipment or inthe worst casesa fire or

To preventpolymerformation inStyrenemonomer,stabilizer is added

4 4 16 Avoid the depletion ofstabilizer concentration,Monitor temperatureregularlyStyrene Monomer storageMaximum Temperature °Frespectively 95 (3 days),85 (2 weeks), 75 (5weeks), 65 (3 months).



79




Catalysts.

Dirt providesseeding sites forpolymer formation

explosion. Necessary steps must betaken to insure adequatecooling of styrene in thestorage tank. At aminimum, all tanks shouldeither be insulated orpainted with a light,reflective paintRefrigeration may beconsidered when no othermeans exist to maintaintank temperatures below75°F.

Less Temperature Lesstemperaturoftank e

Coolingof tank ,moisture engress atvent

Unsafe condition Supervision 3 3 9

Less Pressure Less pressure Fast pumping outand vent blocked

Implosionhazard

Supervision 4 3 15



80




More Pressure Morepressure attank

Polymerization PressurizationExplosion ,Disposal ofpolymerizedStyrene problemPollutionproblem.

VentDisposal toauthorizedagency

5 2 10 Centrifugal pumps mustNEVER be allowed to runwith a closed or throttleddischarge line. This willcause rapid polymerbuildup in the pump case.

All tanks, lines, valves,and pumps should havestyrene monomerrecirculated at least twiceper week to avoid polymerbuildup in the equipment.

Less Composition Liquidphase.

stabilizer leveldepletion(dissolved Oxygenlevel in Styrenemonomer).

Depending ontank conditions,incipientpolymerizationmay occur at thislevel.

Supervision 4 3 15 Stabilizer levels should bemonitored on a routinebasis.



81




More Phase Vaporphase.

Summer season. Styrenemonomer vaporsare not inhibitedand will beoxidized to formpolymer.

Vent 4 4 16 Tank sizing is alsoimportant. Tanks shouldrun as full as possible tominimize vapor spacewhere polymer forms.

More LevelLess Level Less level Depletion of stock

or long shut downLarge vaporspace , increasedpolymerformationUnsafe condition

Shut downprocedures

3 3 9

Other Handling. Spill/ leak. Styrene monomeris a highlyflammable liquid.

LEL 1.1 % UEL6.1 %; Flash point90°F.

The 8-hour TWAoccupationalexposure limit

Fire/ explosionhazard.Incompletecombustion maygeneratedangerousproducts such asCarbonMonoxide.Health hazard

Flameproof area

Styrene odor isdetectable atabout 60 ppm.

5 4 20



82




recommended byACGIH is 20 ppm.The OSHA 8-hourTWA limit is 100ppm.

Other Maintenance MOC Styrene monomer,like otheraromatics, is notcompatible withmost elastomersand rubbermaterials. It also isnot compatiblewithCopper and Copperalloys.

Unsafe conditionin caseincompatiblematerials used

Supervision 3 3 9

83

NODE 2 - ESTERIFICATION

Esterification is the reverse of hydrolysis and leads to an equilibrium reaction, which is thereason that quantitative esterification is possible only by continuous removal of one oftheproducts, i.e. ester or water. In the case of transesterification, an alcohol is released insteadof water. Suitable catalysts are sulphuric acid, hydrogen chloride, arylsulphonic acids such asptoluenesulphonic acid, and chlorosulphuric acid. Phosphoric acid, polyphosphoric acids, andmixtures of acids are also recommended Removal of water usually involves the addition ofentrainers, which form azeotropes with relatively low boiling points and high water contents(usually toluene, xylene, cyclohexane,

Reaction

FLOW CHARTCo-solvent

PHASE SEPARATION

Reaction waterSolventEntrainerAlcohol

AcidAlcoholCatalystEntrainer

ESTERIFICATION

VOC

PRODUCT



84

NODE 2 OF 4 : ESTERIFICATION. EQUIPMENT: ESTERIFICATION REACTOR.DESIGN INTENT :

Guideword


S P R Action

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

Uncontrolledreaction.

Pressurization /explosion hazard.

SOP.

Supervision.

4 3 12

More. Flow. More flowat vent.

Loss of coolingmedium atcondenser.

More flow atcondenser vent.

SOP.

Supervision.

4 3 12

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

Emission atcondenser vent.

SOP.

Supervision.

4 3 12

Reverse

Flow. Reverseflow.

Reverse flow atvacuum line ifpower fails.

Disturbedoperation.

SOP.

Supervision.

3 3 9 Provide NRV in vacuum line.

AsWellAs.

Composition.

Sidereactionproducts

Waste watergenerated in theprocess containsside reactionproducts .

Fire / explosionhazard.

SOP.

Supervision.

4 3 12



85


Guideword


S P R Action

AsWellAs.

Effluent. Effluentgeneration.

Reaction watersolvent entrainedalcohol.

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

Waste streamscan be reducedby recovering(and reusing)any organicsolvents, waterand alcoholcomponents.

3 3 9

AsWellAs.

Emissions. Vent gases. VOC. Emission at vent. Refluxcondenser.

3 3 9

AsWellAs.

Solidwaste.

Solid wastedisposal.

Spent catalyst. Environmentalissues.

Hazardous solidwaste disposal toCHWTSDF.

3 3 9

Other. Flow. Staticcharge.

Static sensitivesolvents are usedas entrained.

Static charge assource of ignition,fire hazard.

Equipments areearthed.

3 3 9 Provide effective measures forprevention of accumulation ofstatic charge to a dangerousextent.

More. Temperature.

Moretemperature.

Reactionexotherm –moderate.

Emission at vent. Process control.

Supervision.

3 3 9



86


Guideword


S P R Action

Less. Temperature.

Lesstemperature.

Not significant. – – –

More. Pressure. MorePressure.

Excessiveheating.

Release offlammable vaporsat vent.

Process control.

Supervision.

3 3 9

Less. Pressure. LessPressure.

Vacuum in thesystem.

Fast pumping outand vent closed.

Fast cooling, ventclosed.

Not significant. Equipments aredesigned forvacuum.

– – –

More. Phase. Morephases.




87


Guideword


S P R Action

AsWellAs.

Composition.

Impurities. Hydrolysisproducts.

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

Process control.

Supervision.

3 3 9

More. Level. More level. Human error.

Excessivecharging of batch.

Entrainment,ingress ofmaterial in ventline.

Sight glass/ glassequipment.

3 3 9 Provide vacuum trap in vacuumline.

Less. Level. Less level. Less batchcharging.

Human error.

Thermowell maynot dip.

Unsafe condition.

SOP.

Supervision.

3 3 9

Other. Handling. MDChandling.

Exposure to MDCvapors.

Health hazard. Fume hoodsprovision.

4 4 16

Minimize exposure to MDCwhile working in view of thetoxic property of MDC.


NODE 3 OF 4: TANK FARM

88

NODE 3 OF 4 : EFFLUENT TREATMENT PLANT

DESIGN INTENT : Effluent treatment

Guideword


S P R Action

None. Flow. No flow ofthethoroughlymixedeffluent tothe ‘SettlingTank’.

Transfer pump(TP) failure /malfunctioning/ power failure.

Valve failure.

Delayedoperation.

Supervision.

SG.

3

3

3

3

9

9

Provide Log book/ records.SOP and check list for transfer.

More. Flow. Morequantityflow toETP.

Large spill inplant.

Fire fightingwater.

Human error.

Filter blockage.

Over flow, spillhazard.

Supervision. 3 3 9

Less. Flow. Lessquantityflow toETP.

Leak overpiping, valuegasket failureetc.

Spill hazard. Supervision. 3 3 9

Reverse.

Flow. Reverseflow.

Not anticipated. - - -



89



Guideword


S P R Action

Aswell as

Effluent Effluentgenerationat processoperations

From Neopentylglycol resinswith high CODcontainingNPG, EG,Allyl alcohol,Acetone ,propionaldehyde, andDioxanes .

Pollution problemFire /explosionhazard due toPropionaldehyde

Treated bydistillationPropionaldehyde(97 % )cut fordisposal toexternal agency2. Distilled watercut to ETP3. Residualglycols

4 4 16

Consider possibility of residualglycol cut recycle in akyd resinsprocess

Aswell as

Effluent Effluentgenerationat processoperations

From Propylenglycol resinswith high CODcontaining G,EG, Allylalcohol,Acetone ,propionaldehyde, andDioxanes .

Pollution problemFire /explosionhazard due toPropionaldehyde

Treated bydistillationPropionaldehyde(97 % )cut fordisposal toexternal agency2. Distilled watercut to ETP3. Residualglycols

4 4 16

Consider possibility of residualglycol cut recycle in akyd resinsprocess



90



Guideword


S P R Action

Aswell as

Composition

Sidereactionproducts inwaste water

Waste watercontainsacetone andpropionaldehyde

Fire /explosionhazard

Aswell as

Composition

Sidereactionproducts inwaste water

Waste watercontainsdioxanes

Lowbiodegradabilityand high odour.

ETP provided

Aswell as

Effluent Effluentgenerationat scrubber

Waste processwater comingfrom waterscrubber andvacuum pumps

High CODeffluent pollutionproblem

Removal ofAldehyde,glycols andacetone.bydistillationfollowed bybiological andchemical watertreatment

3 4 12.



91



Guideword


S P R Action

Aswell as

Effluent Effluentgenerationat floorwashings

Floor washingsof the processarea , firefighting /sprinkler waterOrganicContaminatedwater

Pollution problemOff site potential

4 4 16

Avoid Organic Contaminatedwater entering storm drain ,route the same to ETP .

Aswell as

Hazardouswaste

Hazardouswastegenerationat plant

Generation ofEthylene glycolfrom partialcondensercooler.

Pollution problem Disposal ashazardous wasteto externalauthorizedagencies

3 3 9

Aswell as

Hazardouswaste

Recoveredsolvent

Recoveredsolvent inProcess

Pollution problem Disposal ashazardous wasteto externalauthorizedagencies

3 3 9 Monitor impurity profile of thesolvent stream sent for recovery.



92



Guideword


S P R Action

More Emission Processemission

More Processemission

The ventemission has asweet smell

Water scrubberto condensate themain glycols andact as a bufferwhen there arepeaks ofemissionWork placeMonitoring

4 4 16

Aswell as

Soild waste Soild wastegeneration

Solid particlesfrom coolingwater vacuumring pump.

Hazardous waste Disposal toexternal agencyfor treatment

3 3 9

Aswell as


Solid resincoming fromdraining pipesand reactorsSolid resin fromthe baghouseexhaustcollector.

Disturbedoperation

Recovered in theprocess

2 2 4 . It is recovered in the process.43 mT/year.



93



Guideword


S P R Action

Aswell as


Waste solidresin fromdraining autocleaning filters.Cleaning andmaintenanceprocess

Pollution problem Disposal toexternal agencyfor treatment

3 3 9


Flammablematerialshandling

Static charge assource of ignition


4 4 16

OtherThan.

Flow. Otherstream.

Not anticipated. Dedicatedpiping.

2 1 2

More. Temperature.

Hightemperatureat ETP

Not anticipated. – – –

Less. Temperature.

LesstemperatureAt ETP


More. Pressure. Morepressure.

Not anticipated. Systems open toatmosphere.

– – –



94



Guideword


S P R Action

Less. Pressure. Less pressure. Vacuum notanticipated.

Systems open toatmosphere.

– – –

More. Composition. Incompitablesmix up.

The effluent outflowfrom the variousprocess tank washingand floor washing iscollected in thesetanks, throughcommon header.

Potential for seriousconsequencesdepending up on mixup

Supervision. 4 3 12 Route the spill/floor washingthrough collectionpit for controlledtransfer to ETPfor treatment.

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

Waste accumulationat site.

Sludge will bedisposed by thirdparty (AuthorizedSolid wastemanagementcompany).

3 3 9 .



95



Guideword


S P R Action

More. Level. Higher levelat HoldingcumEqualizingTank.

The effluentoutflow fromthe variousprocess tankwashing andfloor washing iscollected inthese tanks,throughcommonheader.

Overfilling dueto operatorerror.

Overflow. Equalizationtank/Neutralizationtank.

Supervision.

3 3 9

Less. Level. Less level attank.

Human error. Transfer pumpsuction starving.

Supervision. 2 2 4

Other. Handling. Handling ofcorrosivechemicals.

Acid and basesare used.

Injury in case ofsplash.

PPE.

Safety showerand eye washfountain.

3 3 9



96



Guideword


S P R Action

Other. Maintenance.

Repair overinstallation.

Inspection/maintenance.

Residual gas inthe system needto be removed.

Fire/ explosion.

Health hazard.

PPE.

Work permit.

4 3 12



97

NODE 4 OF 4 : OTHER UNIT PROCESSES AND UNIT OPERATIONSDESIGN INTENT :

Guideword



None. Flow. No flow ofnitrogen

Human errorvalve failure

Line blockage

Risk to haveflammableatmospherebetween 110 to140 ºC oftemperature in thekettles andflammableatmosphere in thedistiller whiledistilling lights.explosion hazard.

SOP.

Supervision.

4 3 12

More. Flow. More flowat vent.

Loss of coolingmedium atcondenser.

More flow atcondenser vent.

SOP.

Supervision.

4 3 12

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

Emission atcondenser vent.

SOP.

Supervision.

4 3 12



98


Guideword



Reverse.

Flow. Reverseflow.

Reverse flow atcharging ofpowder rwmaterials atreactor chargingpoint

Emission at workplace

SOP.VentilationSupervision.

3 3 9

AsWellAs.

Effluent. Generationof effluent.

Waste waterstreams fromprocess.ScrubberVacuum pumpFloor washings

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

Specific wastewater volumesare generallylow, effluentsmainly consist ofreaction water ifrecycling afterphase separationis not possible.

ETP provided.

4 3 9



99


Guideword



AsWellAs.

Emissions. Vent gases. VOC.

Reactor emissionsand distillationoperations may bea source ofemissions.

Emissions at vent.

Environmentalissues.

Refluxcondenser.Vent scrubber

4 3 9

AsWellAs.

Solidwaste.

Solid wastegeneration.

Residue. Environmentalissues.

Hazardous solidwaste disposal toCHWTSDF.

3 3 9


Handling of staticsensitive material.

Static charge assource of ignition,fire hazard.


4 4 16

Provide effective measures forprevention of accumulation ofstatic charge to a dangerousextent.

More. Temperature

Moretemperature

More heating inerror

Emission at vent.Decomposition ofglycol toaldehydes andketones

AIT for DEG 2290c

Max temperatureto 290 0c ,limiting due toheating mediamax temperature. The reactionsare endothermic

4 3 12



100


Guideword



AIT for tri butylamine 210 0cUsual thermal oilflash points <lower thanprocesstemperatures

Inerting atreactor

Less. Temperature

Lesstemperature

Lack of heating Solidification ofreaction masse.g Neopentylglycol couldsolidify

Supervision 3 3 9

More. Pressure. Morepressure atthermicfluidsystem

Excessiveheating.All valves closedin error

Release of hot oilat vent.

Expansion tank .Supervision.

3 3 9



101


Guideword



Less. Pressure. Lesspressure.

Vacuum in thesystem.

Fast pumping outand vent closed.

Fast cooling, ventclosed.

Entrainment invent line ,blockage ofcondenserPressurization

Equipments aredesigned forvacuum.

3 3 9

More. Phase. Morephases.

Foaming due tohigh quantity ofwater generation

Entrainment invent line ,blockage ofcondenserPressurization

RDSRVSupervision

4 3 12

AsWellAs.

Composition

Sidereactionsproducts

At hightemperature Sidereactionsproducts areformed

Aldehyde , diglycol ,degradationproducts ofdiester group ,Dioxane &dioxolene

The side reactionproducts arepurged fromwaste watergenerated atscrubber , ventemissionProcess control.Supervision.

4 4 16



102


Guideword



More. Level. More level Human error.Valvemalfunction

Flammablelighter overflowfollowed by firexplosion

Supervision 4 3 12

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

Thermowell maynot dip.Unsafe condition.

SOP.

Supervision.

3 3 9

Other Soft ware DCS , PLCfailure

Soft wareproblem

Unsafe condition PI , TI at allreactors andsecond stagereactors,operation inmnual mode

2 3 6

103

SECTION 3: FAILURE FREQUENCY ANALYSIS

3.1 EVENT TREE – FLAMMABLE SOLVENT RELEASE

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

104

3.2 EVENT TREE – FLAMMABLE GAS RELEASE

Fire/ Explosion frequency = 0.004 + 0.0004 = 0.00440.5 if distance to 50 % LFL falls within plant (with control of company).

105

SECTION 4: CONSEQUENCE ANALYSIS ACCIDENT

4.1 INTRODUCTION

4.1.1 LIKELY ACCIDENT SCENARIOS

TABLE NO. 4.1: LIKELY ACCIDENT SCENARIOS.

1. Butyl Acrylate release.

2. HSD release.

3. Methyl Metha Aacrylate release.

4 Furnace oil release.

5. Styrene release.

6 Xylene release.

These accident scenarios are divided in two categories considering the consequence

seriousness and occurrence frequency.

MAXIMUM CREDIBLE LOSS SCENARIO (MCLS).

WORST POSSIBLE SCENARIO.

4.1.2 MAXIMUM CREDIBLE LOSS SCENARIO (MCLS)

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

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

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

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

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

accident.

The MCLS aims at identifying undesirable and hazardous events causing the

Maximum damage to human beings environment around the industry under

the consideration.

Leak from hose/ tank overflow/ piping failure are quite probable events.

Accidental spill of monomer /Xylene and followed by fire are considered as

MCLS.

4.1.3 WORST POSSIBLE SCENARIO

106

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

Accidental release of Butyl acrylate is considered as Worst Case Scenario/

MCA (Maximum Credible Accident).

4.2 ACCIDENT SCENARIO NO. 1: BUTYL ACRYLATE SPILL

CHEMICAL NAME: BUTYL ACRYLATE 141-32-2

Mole Weight 128.17 g/mol Ambient B.P. 147.3 oC VP. at ambient temp 0.0096 atmERPG-1 0.05 ppm ERPG -2 25 ppm ERPG -3 250 ppm

LEL 12000 ppm UEL 80000 ppmAmbient Saturation Concentration: : 9,647 ppm or 0.96%

SOURCE STRENGTHMax Average Sustained Release Rate: 9.6 grams/min

ACCIDENT SCENARIO NO. 1.1THREAT MODELED

TOXIC AREA OF VAPOR CLOUD

THREAT ZONE

Red ERPG -3 250 ppm. < 10 meters.

Orange ERPG -2 25 ppm. 19 meters.

Yellow ERPG -1 0.05 ppm. 492 meters.

ACCIDENT SCENARIO NO. 1.2

107

THREAT MODELED

FLAMMABLE AREA OF VAPOR CLOUD

THREAT ZONE

Red 7200 ppm = 60% LEL = Flame Pockets. < 10 meters.

Yellow 1200 ppm = 10% LEL. < 10 meters.


THREAT MODELED: OVER PRESSURE (BLAST FORCE)

VAPOR CLOUD EXPLOSION

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

ACCIDENT SCENARIO NO. 1.4 POOL FIRE

THREAT MODELED: POOL FIRE MODEL

S. N. THERMAL RADIATION LEVEL EFFECT DISTANCE

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

2. Distance to 5.0 KW/sq.m (2nd degree burns within 60 sec). < 10 meters.

3. Distance to 2.0 KW/sq.m (pain within 60 sec). < 10 meters.

ACCIDENT SCENARIO 2: DIESEL OIL RELEASE.

THREAT ZONE:

Threat Modeled: Thermal radiation from pool fire.

SR. NO. THERMAL RADIATION LEVEL Affect distance

1. Distance to 37.5 KW/M2 (100 % Lethality). 11 m


3. Distance to 4.0 KW/M2 (Emergency Action). 13.5 m

108

ACCIDENT SCENARIO NO.3: METHYL METH ACRYLATE SPILL

CHEMICAL NAME: METHYL METHACRYLATE Monomer 80-62-6

Mole Weight 100.12 g/mol Ambient B.P. 100.3 oC VP. at ambient temp 0.064 atmPAC-1 17 ppm PAC -2 120 ppm PAC-3 520 ppmIDLH 1000 ppm LEL 17000 ppm UEL 125000

ppmAmbient Saturation Concentration: : 63,727 ppm or 6.37%



THREAT MODELED


THREAT ZONE

Red PAC -3 570 ppm. < 10 meters.

Orange PAC -2 120 ppm. 24 meters.

Yellow PAC -1 17 ppm. 66 meters.

IDLH 1000 ppm < 10 meters.

Note: Threat zone was not drawn because effects of near-field patchinessmake dispersion predictions less reliable for short distances.

109


THREAT MODELED


THREAT ZONE







ACCIDENT SCENARIO NO. 3.4 POOL FIRE

THREAT MODELED: POOL FIRE MODEL





ACCIDENT SCENARIO NO. 4: FURNACE OIL RELEASE.

THREAT ZONE:

Threat Modeled: Thermal radiation from pool fire.

SR. NO. THERMAL RADIATION LEVEL Affect distance


110


3. Distance to 4.0 KW/M2 (Emergency Action). 18 m

ACCIDENT SCENARIO NO. 5: STYRENE SPILL

CHEMICAL NAME: STYRENE MONOMER: 100-42-5

Mole Weight Ambient B.P. 145.2 oC VP. at ambient temp 0.011 atmERPG-1 50 ppm ERPG -2 250 ppm ERPG -3 1000 ppmIDLH 700 ppm LEL 11000 ppm UEL 61000 ppmAmbient Saturation Concentration: 10,878 ppm or 1.09%



THREAT MODELED


THREAT ZONE

Red ERPG -3 1000 ppm. < 10 meters.

Orange ERPG -2 250 ppm. < 10 meters.

Yellow ERPG -1 50 ppm. 14 meters.

IDLH 700 ppm. < 10 meters.

Note: Threat zone was not drawn because effects of near-field patchiness make dispersionpredictions less reliable for short distances.


THREAT MODELED


THREAT ZONE


111






ACCIDENT SCENARIO NO. 5.4 POOL FIRETHREAT MODELED: POOL FIRE MODEL





ACCIDENT SCENARIO NO. 6: XYLENE SPILL

CHEMICAL NAME: o Xylene 95-47-6

Mole Weight 106.17 g/mol Ambient B.P. 144.4 oC VP. at ambient temp 0.012 atmIDLH 900 ppm LEL 11000 ppm UEL 64000ppmAmbient Saturation Concentration: 11,730 ppm or 1.17%

CHEMICAL NAME: m Xylene 108-38-3

Mole Weight 106.17 g/mol Ambient B.P. 139.0 oC VP. at ambient temp 0.015 atmPAC 1 150 ppm PAC 2 200 ppm PAC 3 1000 ppmIDLH 900 ppm LEL 11000 ppm UEL 64000ppmAmbient Saturation Concentration: 14,721 ppm or 1.47%

CHEMICAL NAME: p Xylene 106 -42-3

Mole Weight 106.17 g/mol Ambient B.P. 138.2 oC Ambient freezingpoint

13.3 oC

IDLH 900 ppm LEL 11000 ppm UEL 66000ppmACCIDENT SCENARIO NO. 6.1

THREAT MODELED : TOXIC AREA OF VAPOR CLOUD

THREAT ZONE

IDLH 900 ppm. < 10 meters.

112

Note: Threat zone was not drawn because effects of near-field patchiness make dispersionpredictions less reliable for short distances.

ACCIDENT SCENARIO NO. 6.2THREAT MODELED


THREAT ZONE

Red 60% LEL = Flame Pockets. < 10 meters.

Yellow 10% LEL. < 10 meters.





ACCIDENT SCENARIO NO. 6.4 POOL FIRETHREAT MODELED: POOL FIRE MODEL





NOTE:

1. ATMOSPHERIC DATA

Wind from West at 1.5 m/s Stability Class F Cloud cover 5 tenthNo Inversion Relative Humidity 50 % Air temperature 30 oC

WIND ROSE

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

3. Apart from the maximum credible releases, the conservative approach appears in adoption of atmospheric conditions, usedin the dispersion calculation. In general, the assumptions/ conditions will result in the largest damage distances. Hence, it

113

must be remembered that this analysis will be pessimistic & conservative in approach & is only a planning tool. Its useshould not be extended without understanding its limitations.

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

114

SECTION 5: IMPACT ASSESSMENT

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

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

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

exposed who suffer particular type of injury.

5.1 THERMAL RADIATION IMPACT

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

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

thermal dose that is defined by the function

3

4It .

Where,

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

The probit equation utilized is the Eisenberg equation.

3

4

ln56.29.14 ItY

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

flux exposures.

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

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

FATAL THERMAL RADIATION EXPOSURE LEVELS

RADIATION LEVELKW/m2

SECONDS EXPOSURE FOR A % FATALITY LEVELS

1 % 50 % 99 %

1.6 500 1300 3200

4.0 150 370 930

12.5 30 80 200

37.5 8 20 50

115

EFFECTS OF THERMAL RADIATION ON UNPROTECTED SKIN

RADIATION LEVEL(KW/m2)

DURATION PERIOD SECONDS BEFOREPain is Felt Blistering Starts

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

Below 2.5 Prolonged exposure can. be tolerated.

5.2 OVER PRESSURE IMPACT

EFFECT OF BLAST PRESSURE WAVE

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

0.03 Shattering of asbestos siding.

0.1 Collapse of steel framing panels.

0.3 Shearing of brick walls (8-12 inches)

5.2.1 Lung Hemorrhage

or PP ln91.677

Where,

Po is the Peak Over Pressure (Pa) = 5.1 corresponds to 54 %.

5.2.2 Ear Drum Rupture

or PP ln93.16.15

Where,

Po is the Peak Over Pressure (Pa) = 4.0 corresponds to 15 %.

5.2.3 Fatality Due To Impact

or PP ln82.41.46

Where,

Po is the Peak Over Pressure (Pa).

= 2.3 corresponds to 0 %.5.2.4 However over pressure of 3.5 psi at site will affect up to <10 m.

116

5.3 TOXICITY IMPACT

BUTYL ACRYLATE

The material can cause respiratory irritation in some persons. The body's responseto such irritation can cause further lung damage.

Inhalation of vapours may cause drowsiness and dizziness. This may beaccompanied by narcosis, reduced alertness, loss of reflexes, lack of coordinationand vertigo.

Inhalation of vapors or aerosols (mists, fumes), generated by the material duringthe course of normal handling, may be damaging to the health of the individual.

Inhalation hazard is increased at higher temperatures. If exposure to highly concentrated vapor atmosphere is prolonged this may lead to

narcosis, unconsciousness, even coma and unless resuscitated - death. The main effects of simple esters are irritation, stupor and insensibility. Headache,

drowsiness, dizziness, coma and behavioral changes may occur. Respiratorysymptoms may include irritation, shortness of breath, rapid breathing, throatinflammation, bronchitis, lung inflammation and pulmonary edema, sometimesdelayed. Nausea, vomiting, diarrhea and cramps are observed. Liver and kidneydamage may result from massive exposures.

BUTYL ACRYLATE

Half- life Soil - High (hours): 168 Half- life Air - High (hours): 23 Half- life Surface water - High (hours): 168 Half- life Ground water - High (hours): 336 Aqueous biodegradation - Aerobic - High (hours): 168 Aqueous biodegradation - Anaerobic - High (hours): 672 Photooxidation half- life air - High (hours): 23 First order hydrolysis half- life (hours): 307000

STYRENE MONOMER/ Ethylbenzene degrades rapidly in the environment and does

not significantly bio-accumulate. It floats on water and rapidly evaporates. It is not

expected to adsorb to sediment and suspended solids in water. Ethylbenzene is readily

biodegradable and is expected to undergo full mineralisation in the aquatic

environment under aerobic conditions within days to a few weeks. Direct hydrolysis

or photolysis is not expected. In the atmosphere ethylbenzene will be degraded by

photo chemically produced hydroxyl radicals with a half-life of about 2 days.

117

SECTION 6: RISK ESTIMATION

6.1 INDIVIDUAL RISK ISOPLETH

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

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

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

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

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

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

measures have different values.

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

iyxyx IR

NIR ,,,

1

Where,

N is number of persons in the affect zone.

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

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

of heat flux or greater.

6.1.3 VULNERABLE ZONES

Vulnerable zones for various accident scenarios are superimposed on the plot

plan and enclosed in Section No. 1.

Refer section 1.13.1 .

6.1.4 RISK ISOPLETH

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

injury to personnel (assuming two persons working in the area).

118

INDIVIDUAL FATALITY QRA RESULTS.

INDIVIDUALFATALITY (IR)

DOWNWIND AFFECTDISTANCE (m) REMARKS

1.0 × 10-4 per yr. <10 This contour remains on-site.1.0 × 10-5 per yr. <10 This contour remains on-site.1.0 × 10-6 per yr. <10 This contour remains on-site.

A broadly acceptable level of individual risk as per the ALARP (As low as reasonablypracticable) concept of HSE, UK is 10-6/ year.

INDIVIDUAL FATALITY CRITERIA

Individual Fatality (IR) Individual Fatality Criteria1 × 10 -4 per year This contour remains on-site.1 × 10 -5 per year This contour extends into industrial

developments only.1 × 10 -6 per year This contour extends into commercial and

industrial developments only.

6.2 SOCIETAL RISK (F – N CURVE)

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

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

aNkF Where,

F = the cumulative frequency of N or more fatalities.

N = the number of fatalities.

a = aversion factor (often between 1 and 2).

k = constant.

The slope of the societal risk criterion (when plotted on a log – log basis) is equal to

‘–a’ and represents the degree of aversion to multi-fatality events embodied in the

criterion. When the F – N curve slope is equal to -1, the risk criterion is termed ‘risk

neutral’. A risk criterion for which the curve slope is more negative than -1 is said to

be more risk averse. An anchor point along the curve (e.g. N=10 fatalities,

F=10-3/year) and a slope (e.g. -1) is usually enough information to plot a risk criterion

F – N curve. if any portion of the calculated F – N curve exceeds the criterion line, the

119

societal risk is said to exceed that risk criterion. In the present case the slope is

negative and the curve is well below the criterion line indicates insignificant societal

risk.

SITE SURROUNDINGS – MIDC AREA.

Refer section 1.13.3 in Section No. 1.

.

SITE SURROUNDING.


.

` Predominant direction of wind at site is from South – West Side.

F/N CURVE


SECTION 7: RISK MITIGATION MEASURES

Refer Section 1.15

120

ANNEXURE 1: GLOSSARY

AcceptanceCriteria (Risk).

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

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

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

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

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

HazardousScenario

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

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

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

121

Individual RiskContours.

: As IR (Individual Risk) is calculated at a point, calculating the IR at many pointsallows the plotting of IR contours, these being lines that indicate constant levelsof risk. Most commonly used are the 1 chance per million-year contour and the10 chances per million-year contour.

Individual RiskOf Fatality.

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

Individual RiskOf Injury.

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

IsolatableSection.

: A system of pipes or vessels containing the hazardous materials that arebounded by specific isolation points.

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

LEL. : Lower Flammability Limit.Expressed as % by volume of flammable gas in air. This is the minimumconcentration of gas in air mixture which can ignite. Gas air mixtures below thisconcentration do not ignite.

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

QuantitativeRisk Assessment.

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

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

Risk Reduction. : The process of risk assessment coupled to a systematic consideration ofpotential control measures and a judgment on whether they are reasonablypracticable to implement.

122

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

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

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

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

Vapor CloudExplosion

: An accidental release of flammable liquid or gas, there is possibility that it mayform a cloud which can spread along the wind direction. Delayed ignition of thecloud away from the source of release results in Vapor cloud explosion (flashback) and associated blast / over pressure effects.

123

ANNEXURE 2: ABBREVIATIONS

AIChE. American Institute Of Chemical Engineers.ALARP. As Low As Reasonably Practicable.BTU. British Thermal Unit.CCPS. Centre For Chemical Process Safety.DMP. Disaster Management PlanECC. Emergency Control Centre.EIA. Environmental Impact Assessment.EMP. Environment Management Plan.F & E I. Fire And Explosion Index.FIG. Figure.HAZOP. Hazard Operability.HSD. High Speed Diesel.IDLH. Immediately Dangerous To Life And Health.IPL. Independent Protection Layer.KCal. Kilocalories.lb. Pound.LOC. Level Of Concentration.LOPA. Layers Of Protection Analysis.MCA. Maximum Credible Accident.MF. Material Factor.MIDC. Maharashtra Industrial Development Corporation.MoEF. Ministry Of Environment And Forests.MSDS. Material Safety Data Sheet.MT. Metric Ton.NFPA. National Fire Protection Association.PFD. Probability Of Failure On Demand.PHA. Preliminary Hazard Analysis.QRA. Quantative Risk Assessment.RH. Risk Assessment And Hazard Management.SIF. Safety Integrated Function.TEEL. Temporary Emergency Exposure Limits.UK. United Kingdom.

124

ANNEXURE 3: REFERENCES

1. Technical EIA Guidance Manual for Synthetic Organic Chemicals,

prepared for the Ministry of Environment and Forests Government of

India.

2. MOND INDEX Manual 1993.

3. “TNO Yellow Book”. Method for calculation of the Physical Effects of

the escape of Dangerous Material (Liquid & Gases) Published by the

Directorate General of Labour, Ministry of Social affair, Netherlands

(1979).

4. Frank P. Lees – Loss Prevention in the Process Industries – Volume I.

5. Risk Assessment for Process Industries, Loss Prevention News April -

June 2001.

6. Techniques for assessing Industrial Hazards (World Bank Technical

Paper, ISSN 0253; No. 55).

7. Ref. Table 3.8 – Vapor Pressure of Organic Compounds, R. H. Perry,

C.C., Chemical Engineers Handbook, 5th Edition (1969) McGrow – Hill

Book co. (New York, London).

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

9. Fire Protection Manual of TAC: 1982; 9th Edition.

10. OSID –STD -116 amended edition – October, 2002.

11. The Maharashtra Fire Prevention and Life Safety Measures Act, 2006.

Documents

RISK ASSESSMENT - environmentclearance.nic.inenvironmentclearance.nic.in/writereaddata/FormB/EC/Risk_Assessmen… · 1.2 THE ASSIGNMENT Mr. Subhash Bonde ... Expert – Risk Assessment