PVC EDC Polyethylene LdHd Ethylene EDC EO EG

ΔΕΝΔΡΟ ΠΑΡΑΓΩΓΗΣ ΠΕΤΡΟΧΗΜΙΚΩΝ Δομικά προϊόντα Ενδιάμεσα προϊόντα Τελικά προϊόντα PVC EDC Polyethylene (Ld/Hd) Ethylene EDC EO EG DMT PVC PBR SBR - Ethylene dichloride Ethylene oxide Ethylene glycol Dimethyl terephathalate Polyvinyl chloride Polybutadiene rubber Styrene butadiene rubber EO/EG Isopropyl Alcohol/ Acetone Propylene Polypropylene 2 Ethyl Hexanol A B S Plastics PBR SBR Butadiene Cumene/Phenol Cyclohexane/ Caprolactum Naphtha Dye Stuff and Chemicals Intermediate Acrylonitrile Acrylic Fiber Olefins Glycol Ethers Enthaloamines Benzene Detergents Alkylate Plasticisers Pharmaceuticals Thermoset Resins Nylon Detergent Polyester Aromatics Maleic Anhydride Phthalic Anhydride Xylene DMT Alkyd Resins Plasticisers Polyester Fibre

ΠΑΡΑΓΩΓΗ ΥΓΡΩΝ ΑΠΟΒΛΗΤΩΝ BOD 0, 38 Kg/tn oil COD 1, 18 Kg/tn oil Oil 0, 17 Kg/tn oil Phenolic compounds 0, 03 Kg/tn oil TSS 0, 24 Kg/tn oil NH 3 0, 18 Kg/tn oil H 2 S 0, 21 Kg/tn oil COD/BOD 3, 2 Kg/tn oil

ΚΡΙΤΗΡΙΑ ΤΟΞΙΚΟΤΗΤΑΣ Score 10 7 4 0 Oral LD 50 (mg/l) <5 > 5 to < 50 > 50 to < 500 > 500 Dermal LD 50 (mg/l) <5 > 5 to < 500 > 500 Acute LD 50 (mg/l) <1 > 1 to < 10 > 10 to < 100 > 100 DDB SLIDES

ΠΡΟΤΕΡΑΙΟΤΗΤΑ ΧΗΜΙΚΩΝ ΕΝΩΣΕΩΝ Ονομα χρήση Benzidine Dye Intermediate P-Amino azobenzene Dye Intermediate P-Chloro-o-Nitro Aniline Dye Intermediate O-Chloro Phenol Dye / Drug Intermediate P-Chloro Phenol Dye / Drug Intermediate 3, 4 - Dichloro aniline Dye / Drug Intermediate Hydroquinone Dye Intermediate C. I Basic Violet 1 Dye stuff C. I Pigment Red 3 Dye Stuff 2, 4 - Dichloro Phenol Pesticide / Drug Intermediate Dibutyl Phthalate Drug Intermediate Hydrazo Benzene Drug Intermediate DDB SLIDES

ΚΡΙΤΗΡΙΑ ΚΑΤΗΓΟΡΙΟΠΟΙΗΣΗ των VOCs • Ικανότητα φωτοχημικής οξείδωσης Photochemical Oxidant Creation Potential (POCP) • Δυναμικό συμβολής στο φαινόμενο θερμοκηπίου Global Warming Potential (GWP) • Δυναμικό ελάττωσης όζοντος Ozone Depleting Potential (ODP) • Threshold Limit Value (TLV) • International Agency for Research in Cancer (IARC) Classification DDB SLIDES

ΠΗΓΕΣ ΕΚΠΟΜΠΩΝ VOCs ΣΕ ΔΙΕΡΓΑΣΙΕΣ ΠΕΤΡΟΧΗΜΙΚΩΝ ΚΑΙ ΠΟΛΥΜΕΡΩΝ S. No. Παραγωγή Αναμενόμενος ρύπος 1 Ethylene / Propylene 2 Butadiene Butylene / Propylene 3 Benzene / Toluene / Xylene Benzene / Toluene / o, m, p - Xylene 4 Methanol 5 Ethylene Oxide / Ethylene Glycols 6 Ethylene Glycols Mono, do, tro ethylene glycols 7 EDC / VCM EDC, Ethyl Chloride, Vinyl Chloride, Ethylene, Hydrogen Chloride, Chlorine 8 Vinyl Acetate Monomer Acetaldehyde, Ethylene, Acetic Acid 9 Propylene Oxides / Glycols Propylene oxide, propylene glycol, Epichlorohydrin 10 Acrylonitrile, Hydrogen cyanide, Acetonitrile, Nitrogen Oxides 11 Isopropanol Acetaldehyde, Ethyl Benzene, Acetophenone, Isopropyl Benzene, Methyl Ethyl Ketone, 12 Phenol / Acetone Phenol, Acetone, Cumene DDB SLIDES

ΚΑΤΗΓΟΡΙΟΠΟΙΗΣΗ ΤΩΝ VOC’S v 15 είναι μεγίστης προτεραιότητας v 17 είναι μεσαίας προτεραιότητας και v 20 είναι χαμηλής προτεραιότητας ΚΑΤΑΛΟΓΟΣ ΜΕΓΙΣΤΗΣ ΠΡΟΤΕΡΑΙΟΤΗΤΑΣ VOC’s 1. 3. 5. 7. 9. 11. 13. 15. 1, 3 Butadiene Toluene Vinyl Chloride Acrylonitrile Maleic anhydride TDI Epichloro hydrin Phosgene 2. 4. 6. 8. 10. 12. 14. Benzene Ethylene oxide Propylene oxide Caprolactum Phthalic anhydride Carbon tetra chloride Hydrogen cyanide DDB SLIDES

ΠΑΡΑΔΕΙΓΜΑ ΕΚΠΟΜΠΩΝ ΈΝΑ ΕΡΓΟΣΤΑΣΙΟ ΠΑΡΑΓΩΓΗΣ 300, 000 TPA ΟΛΕΦΙΝΩΝ S. NO 1 2 3 4 5 POLLUTANT SULPHUR OXIDES(SO 2) PARTICULATES (SPM) CARBON MONOXIDE (CO) NITROGEN OXIDES (NOX) VOLATILE ORGANIC COMPOUNDS (VOC’S) POLLUTANT LOAD (KG/DAY) 25 -90 700 -1200 250 -900 1100 -2500 2400 - 4000

v PETROCHEMICAL EMISSION OVERVIEW Ø IT IS EVIDENT THAT EMISSION FROM PETROCHEMICAL COMPLEX IS UNIQUE • LESS CONVENTIONAL AIR POLLUTANTS (EXCEPT NOX) • LARGE VOLATILE ORGANIC COMPOUNDS (VOC) EMISSION • SOME OF THESE VOC’S ARE EXTREMELY HAZARDOUS TO HEALTH (VOC –HAPS) LOCAL CRITICAL CRITERIA • SOME OF THESE VOC’S PARTICIPATES IN COMPLEX REACTION WITH NOX IN ATMOSPHERE AND RESULTS IN PHOTOCHEMICAL OZONE CREATION POTENTIAL (POCP) –LOCAL CRITERIA • VOC’S (VIZ METHANE, N 2 O RESULTING IN GLOBAL WARMING POTENTIAL (GWP) GLOBAL CRITERIA • VOC’S COMPLEX INTERACTION IN ATMOSPHERE AND RESULTING IN STRATOSPHERIC OZONE DEPLETION (SODP) POTENTIAL – GLOBAL CRITERIA Ø LOCAL CRITERIA VIZ VOC-HAP’S AND POCP DEMANDS FOR IMMEDIATE ATTENTION

WHY LDAR PROGRAM DOMINANT VOC EMISSION SOURCES AND ITS TYPICAL DISTRIBUTION FROM A PETROCHEMICAL COMPLEX S No Emission Source Typical Distribution Source Classification General Control Techniques 1 Process Vents 5 -20 Point Source Flare, Incinerator, Restrict, Recycle / Recovery etc 2 Process Equipment Leaks 40 -70 Fugitive (Non Point Source) LDAR, Modification and / or High Integrity Equipment 3 Storage Tanks 5 -15 Point Source Improved Equipment / Seal Design, Recovery as Fuel gas etc 4 Loading Stations 15 -20 Point Source Vapour Recovery, Modification, Flare 5 Waste Water Collection and Treatment 10 -15 Fugitive (Non Point Source) Closed System Improved System Modifications Design, System

WHAT IS LDAR PROGRAMME • LEAK DETECTION AND REPAIR (LDARR) IS AN IMPROVED O&M APPROACH TO RESTRICT/MINIMIZE VOC FUGITIVE EMISSION RESULTING FROM EQUIPMENT LEAK • FOLLOWING INTRODUCTION OF STATUTORY REGULATION AND STANDARDS ADDRESSING VOC EMISSIONS WORLDWIDE DURING EARLY 90’S, LDAR PROGRAM HAS RECEIVED WIDE ACCEPTANCE IN PETROCHEMICAL REFINERIES, PETROCHEMICALS, PHARMACEUTICAL AND FINE CHEMICAL INDUSTRIES • LDAR PROGRAM ARE BEAST APPLIED TO EQUIPMENT AND/OR PIPING SYSTEM / ACCESSORIES THAT CAN BE REPAIRED “ON-LINE’ AND THUS RESULTING IN AN IMMEDIATE EMISSION REDUCTION INVOLVING MINIMUM COST AND TIME. FURTHER; WHERE EQUIPMENT/SYSTEM MODIFICATIONS ARE NOT FEASIBLE – THE LDAR PROGRAM IS THE VIABLE SOLUTION • LDAR PROGRAM IS BEST SUITED FOR THE FOLLOWING EQUIPMENT / SYSTEM = PUMPS VALVES = PIPING / CONNECTOR SYSTEM

VOC CLASSIFICATION VOC HAP’S ARE CLASSIFIED BROADLY IN TWO GROUPS BASED ON IARC WITHIN GROUP CLASSIFICATION WITHIN GROUP --- CARCINOGEN WITHOUT THRESHOLD VALUES ( CLASS – A) --- CARCINOGEN WITH THRESHOLD VALUES ( CLASS –B) PETROCHEMICAL PRODUCTS/COMPOUNDS CLASSIFIED AS VOC –HAP’S VOCHAP CLASS SOURCE (MASS FLOW) IN GM/HR SOURCE EMISSION Mg/NM 3 ATM / GLC MAX EMISSION CONC NANOGM/m 3 COMMON PETROCHEM PRODUCTS / COMPOUNDS A 0. 5 TO 25 0. 1 TO 0. 50 1. 0 TO 100 ETHYLENE OXIDE (EO), ACRYLONITRILE(CAN), BENZENE, BUTADIENE, EPICHLOROHYDRIN (ECH), PROPYLENEOXIDE(PO), EDC / VCM, EPOXYPROPANE (EOP) B 100 20 400 FORMALDEHYDE, HYDRAZINE, ACRYLIC ACID, ANILINE, BISPHENOL –A, PHENOL, PYRIDINE ETC

OTHER VOC’S ARE CLASSIED AS GENERAL BASED ON THEIR POTENTIAL FOR POCP AND OTHER GLOBAL EFFECTS VIZ GWP, SODP ETC VOC – General Class Source, Mass Flow in Gm/Hr Source Mass con. Mg/Nm 3 Atm. Viz. Emission conc. (µg/m 3) (GLCMAX) Example Petrochemical Compounds 1. 0 2000 1. 0 Acetic acid, Butanol, DEA, Cyclohexanol, Methyl Glycol, Toluene, Vinyl acetate etc. 2. 0 3000 – 5000 150 – 250 1. 5 – 3. 0 Ethylene, Ethanol, Ether, Acetone, Iso-butene, Methanol, Olefinic – Hydrocarbon, Isopropanol etc.

PROCEDURE FOR LEAK EMISSION INVENTORY THERE ARE FOUR ESTABLISHED PROCEDURE: v v AVERAGE EMISSSION FACTOR SCREENING RANGE APPROACH EPA CORRELATION APPROACH UNIT SPECIFIC CO-RRELATION APPROACH

TYPICAL APPLICABLE AVERAGE EMISSION FACTOR FOR VARIOUS TYPE OF EQUIPMENT VIS-À-VIS SCREENING RANGE S. No. Equipment type Process Fluid Service Emission factor in (kg/hr/source) Screening valve at 10, 000 ppm (v) Screening valve at 1000 – 10, 000 ppm (v) 1 Valves Gas 0. 0782 0. 000131 2 Valves Light liquid 0. 0892 0. 00165 3 Valves Heavy liquid 0. 00023 4 Pump Seal Light liquid 0. 243 0. 00187 5 Pump Seal Heavy liquid 0. 216 0. 00210 6 Compressor Seal Gas 1. 608 0. 0894 7 Relief Valve Gas 1. 691 0. 0447 8 Piping Connector, Flanges Gas / Light liquid 0. 113 0. 000085 9 Open ended piping Gas / Light liquid 0. 012 0. 00150