Proposed Waste Classification Criteria of Chemicals released from - - PowerPoint PPT Presentation

Proposed Waste Classification Criteria of Chemicals released from Chemical Accidents : Development of Selection Criteria as Designated (Special Care) or Non-designated Chemicals

Distinguished Professor Byeong-Kyu Lee, Ph.D. Ryeo Gyeong Youn, Sang Yong Jang, Yongsun Im

• Dept. of Civil and Environmental Engineering

University of Ulsan, Ulsan, Korea

Chemicals in Daily Life

http://www.pressian.com/news/article.html?no=121215

4

Seveso, Italy, 1976

• Manufacture of a bactericide
• Runaway reaction
• Emission of TCDD with dioxin
• No fatalities, 447 burns, 737 long term

evacuations

• Severe environmental damage
• Lack of information, no proper emergency

plan

Source: Ike Van der Putte, Overview of Seveso Directive and Safety Report Requirement, EUROTOX (2014)

Major Industrial Disaster

Bhopal UC plant, 1984

• Pesticide (carbaryl) production.
• Water entered a tank containing 42 tons of

MIC.

• The resulting exothermic reaction increased T

inside the tank to over 200 C and raised P. The tank vented releasing toxic gases into the Atmosphere.

• Estimates vary on the immediate death toll

(3000-15000)

• A series of explosions occurred on November 13, 2005 at the Number 101 Petrochemical Plant in Jilin City, China.
• The chemical plant’s explosions occurred for over an hour and affected hundreds of thousands of people throughout

the Jilin province and the rest of Asia.

• The blast and the subsequent fire killed at least six people and injured around 70 people.
• Released into the river about 100 tons of benzene.
• The explosion eventually created an 80 km long toxic chemical slick made up of benzene, nitrobenzene, and aniline.
• The chemical slick made its way up the Songhua River, affecting large parts of China and eventually made its through

the Amur River and where it made its way through Russia.

2005 Jilin Chemical Plant Explosion, China

https://disasteropedia.wikispaces.com/2005+Jilin+chemical+plant+explosions

Kumi

Kumi Nat’l IC

Chemical Accidents in Korea, 2012

• 2012. 09. 27, 15:43

HVG in Kumi Nat’l Ind. Complex Hydrofluoric acid (HF) release (8 T)

During charging from 20T- HF tank lorry to storage tank in HVG, 8T HF was released.

Damage : 5 died, 18 injury

HF Release in Kumi

Characteristics of Chemical Accidents

Toxic gas Diffusion Hazardous chem. Leaks

• Environ. Pollution

Suffocation by Combustion Gases Radiative Heat Building Collapse

Simple Fire => Physical Treatment Simple Fire => Physical Treatment Chemical Disaster => Comprehensive Treatment Chemical Disaster => Comprehensive Treatment

▶ Complicated damages → Multiple agency involved ▶ Improper initial response → Fatal environ. disaster ▶ Direct costs < indirect costs ▶ Specialized response

5-year Study Scope and Goals

• 1st year : Development of Management and Control Strategies of Chemicals

released from Chemical Accidents, Fire, and Explosions in industries and during Chemical Transports

• 2nd year : Analysis of Information, Damage, and Control Strategies of

Hazardous Chemicals associated with Chemical Terrors

• 3rd year : Analysis of Accident features, Damage, and Control Strategies of

Agricultural Chemicals during their Transports and Manufacturing

• 4th year : Survey of contaminated facilities/wastes and their treatments of

hazardous chemicals (69 hazardous, terror and agricultural chemicals)

• 5th year : Proper prevention materials against chemicals (69 hazardous,

terror and agricultural chemicals) from chemical accidents and disposal methods of chemicals and contaminated facilities

Total Chemical Emissions in Korea

(Air: 99.3%, PRTR Data, 2014, http://ncis.nier.go.kr/triopen/)

10.000 20.000 30.000 40.000 50.000 60.000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Total Emissions (Tone/yr)

Year

• No. of Chemical Accidents

Year

Number of Chemical Accidents in Korea

Damage from Chemical Accidents in Korea

Year Classification Casualty and cost 2012 human damage death 11 people injury 47 people material damage 55.4 M US$ 2013 human damage death 11 people injury 70 people material damage 5.1 M US$ 2014 human damage death 4 people injury 234 people material damage 0.18 M US$ 2015 human damage death 9 people injury 97 people material damage 0.16 M US$ 2016 human damage death 5 people injury 120 people material damage 0.37 M US$

• No. of Chemical Accidents

출처: 이지윤, 우리나라 화학물질관리 정책방향, 한국화학물질관리협회, (2014)

• 1990~2009: Total 1,487 cases (Average: 74 cases/year)
• Release (478 cases: 32.5%), Fire (396 cases: 26.9%), Explosion (360cases: 24.5%),

Miscellaneous (116 case: 7.9% Release +Fire + Explosion)

Analysis of Chemical Accident Types in Korea

Release Fire Explosion

• No. of Accidents

Miscellaneous Manufacturing In use Storage Transport Sale

Business Types of Chemical Accidents in Korea

Source Analysis of Chemical Accident in Korea

Work processes Storage tanks Road Vehicles Sea Miscellaneous

Cause Analysis of Chemical Accidents in Korea

Improper management

• f facilities

Worker’s carelessness Vehicle accidents Miscellaneous

No wearing Safety Gears Ignorance of work procedure Worker fatigue

HF Release case in Kumi (5 died) ∵ No mask/safety clothes worker HF Release in SS (1 died)

∵ No mask worker

HF Release case in Cheongju ∵ During checking without using ladder, worker fell down and cracked pipes, then released HF To make shorten the term of work in D (6 died) ∵ Excessive work (DOL Survey: Ind. Regulation violation)

Ignorance of safety manuals

Causes of Chemical Accidents in Korea

Easiness/Economy Consideration

Lack of Chemical Knowledge Old Facilities

handy/low price valves use H2SO4 corroded H2O2 Pipes

»Mixing acids, produced persulfuric acid

same as TATP explosives raw materials (triacetone triperoxide, primary high explosive)

Pipe corrosion/abrasion

Inappropriate Handling

Causes of Chemical Accidents in Korea

Inappropriate Loading Lack of driver’s knowledge Difficulty transport tracking

Dangerous Transport Habits

Causes of Chemical Accidents in Korea

Excessive/Open /Untided Loading Dangerous/Explosive Chemicals/s Tap water resource area/ Residential area parking

Class MSDS characteristic Score

E1 Explosiveness + Flammability + Reactivity with water + pH (0 - 5) 0 -10 (extremely) + 0 – 5 (extremely) ) + 0 – 5 (extremely) + 0 – 5 (extremely acidic or basic) E2 E1 + Self reactivity + Self exothermic + Oxidative (explosive) + Carcinogenesis E1 + 0 – 5 (extremely) + 0 – 5 (extremely) + 0 – 7 (extremely) + 0 – 5 (extremely)

Classification by Scoring of MSDS Characteristics

Q = Amount of waste (kg) D = Small amount standard for hazardous chemical substance (Daily handling, kg)

Analysis of E1, E2 score Generation of wastes contaminated by chemicals Max score in E1 Max score in E2

Designated waste

≧ E1 ≧ 10 ≧ E2 ≧ 15

Designated waste

General waste

Q<D Yes Q≧D Q≧D Q≧2D Q<2D Q<D Q<D/2

Classification by MSDS Scores (Designated vs. General)

Q≧D/2 Yes Yes Yes Yes N0 N0 N0 N0

National Fire Protection Association : NFPA (NFPA 704 Marking System)

건강 위험성 반응성 화재 위험성 특수 위험성

4 2 ₩ OX

National Fire Protection Association : NFPA

score check NFPA code 4 (one or

more)

4 (one or

more) Or 3 (two or more)

3 + 3 (one) + Special hazard General waste Designated waste

N N Y Y

Classification by NFPA Code Score (Designated vs. General)

Class Score of Solution pH Class pH Criteria Score 1 pH≧12.5 pH≦2 4 2 11≦pH<12.5 2<pH≦3 3 3 10≦pH<11 3<pH≦4 2 4 9≦pH<10 4<pH≦5 1 5 8≦pH<9 5<pH≦6

▪ NFP A Code Class + pH ▪ Korean regulation: Designated Waste STD (pH ≧ 12.5, pH ≦ 2)

Classification by pH Score to fit NFPA Code (Designated vs. General)

score check NFPA code and pH 4 (≥ 1 item) Or 3 (≥ 2 items) 3 (1 item) + 3 (1 item) +

Special hazard Or ∑(NFPA+pH) ≥9)

General waste Designated waste

N N Y Y

Classification by NFPA Code and pH Scores

(Designated vs. General)

score check NFPA code and pH 4 (≥ 1 item)

Or 3 (≥ 1

items) ∑ )

3 (1 item) +

Special hazard

Or

∑(NFPA+pH)≥9)

General waste Designated waste

N N

Y Y

Type of chemical accident

Explosion/Fire Leakage Q≥D Q≥D/2

Y

Y

N N

Q = Amount of waste (kg) D = Small amount standard for hazardous chemical substance (Daily handling, kg)

Classification by NFPA Code and pH Scores + Waste Quantity to be disposed (Designated vs. General)

Accident causing material Health Fire Reactivity Specific Designated pH Condition (more than) 1 acrolein 4 3 3 ㅇ 2 acrylic acid 3 2 2 ㅇ 2 3 acrylonitrile 4 4 2 ㅇ 4 acrylyl chloride 3 3 ㅇ 5 allyl alcohol 3 3 1 ㅇ 6 allyl chloride 3 3 1 ㅇ 7 ammonia 3 1 1 ㅇ 3 8 Ammonium nitrate 1 3 ㅇ 3 9 Arsine 4 4 2 ㅇ 10 benzene 2 3 ㅇ 3 11 benzyl chloride 3 2 1 ㅇ 3 12 butylamine 3 3 ㅇ 13 carbon disulfide 3 4 ㅇ 14 carbon monoxide 4 4 2 ㅇ 15 chlorine 3 OX ㅇ 16 chlorine dioxide 3 4 OX ㅇ 17 chlorosulfonic acid 4 2 \,OX ㅇ 18 Cyanogen chloride 4 2 ㅇ 19 diborane 3 2 ㅇ 3 20 ethyl acetate 4 4 3 ㅇ Accident causing material Health Fire Reactivity Specific Designated pH Condition (more than) 21 ethyl methyl ketone perox ide 2 4 ㅇ 22 ethylene oxide 3 4 3 ㅇ 23 ethylenediamine 3 3 ㅇ 24 ethyleneimine 4 3 3 ㅇ 25 fluorine 4 4 \,OX ㅇ 26 formaldehyde 3 4 ㅇ 27 formic acid 3 2 1 ㅇ 3 28 Hexamine 1 1 ㅇ 4 29 hydrogen chloride 3 1 ㅇ 3 30 hydrogen cyanide 4 4 1 ㅇ 31 hydrogen flouride 4 1 ㅇ 32 hydrogen peroxide 3 2 OX ㅇ 33 hydrogen sulfide 4 4 ㅇ 34 isophorone diisocyanate 2 1 1 \ ㅇ 3 35 meta-cresol 36 methanol 1 3 ㅇ 3 37 methyl acrylate 3 3 2 ㅇ 38 methyl chloride 2 4 ㅇ 39 methyl vinyl ketone 1 3 ㅇ 3 40 methylamine 2 2 4 OX ㅇ

Classification by NFPA Code and pH Scores (Designated vs. General)

Accident causing material Health Fire Reactivity Specific Designated pH Condition (more than) 41 methylethylketone 4 3 2 ㅇ 42 methylhydrazine 4 3 2 ㅇ 43 nitric acid 3 4 ㅇ 44 Nitric oxide 4 1 OX ㅇ 45 Nitrobenzene 3 3 OX ㅇ 46 nitrobenzene 3 2 1 ㅇ 3 47 phenol 2 3 4 ㅇ 48 phosgene 3 1 1 ㅇ 3 49 phosphine 3 2 COR ㅇ 50 phosphorus oxuchloride 4 1 ㅇ 51 phosphorus trichloride 4 4 2 ㅇ 52 p-nitrotoluene 4 2 \ ㅇ 53 Potassium chlorate 4 2 \ ㅇ 54 Potassium perchlorate 2 3 OX ㅇ 55 Potassium perchlorate 1 OX ㅇ 3 Accident causing material Health Fire Reactivity Specific Designated pH Condition (more than) 56 Potassium permangante 1 1 OX ㅇ 3 57 propylene oxide 2 OX ㅇ 3 58 Sarin 3 4 2 ㅇ 59 sodium 3 3 2 \ ㅇ 60 Sodium chlorate 2 3 OX ㅇ 61 sodium cyanide 4 ㅇ 62 Sodium nitrate 1 OX ㅇ 3 63 sulfuric acid 3 2 \ ㅇ 64 toluene 2 3 ㅇ 3 65 toluene-2, 4-diisocyanate 3 1 2 ㅇ 3 66 triethylamine 3 3 ㅇ 67 trimethylamine 3 4 ㅇ 68 vinyl chloride 3 4 2 ㅇ 69 zinc phosphide 3 3 1 ㅇ

Classification by NFPA Code and pH Scores (Designated vs. General)

Consideration of Current Laws or Regulations with Q

( ) 4 ( ≥ 1 item)

Or 3 ( ≥ 2 items)

Accident Type Explosion Release

Q = Contaminant Quantity D = Small Quantity of Haz. Mat. (Daily Handling STD, Kg)

Waste (Chemical, Facility)

Waste

Management

• Ind. Safety and

Health Law NFPA code Waste Classification Q≥D Q≥D/2 NFPA Code, pH Score Check General Designated

NO NO YES YES

∑( p ) ) 3 (≥ 1 item) + Special Hz ∑(NFPA+pH) ≥ 9)

YES NO YES NO

Regulations of Waste Management Law

Large Category Medium Category Small Category Memo

• 1. Specific site waste

․Waste Polymers ․Waste resin ExcludeSolidstate ․Waste rubber ․Sludge : Moisture [(<95%

• r Solid content (<5%)]

․Wastewater sludge Defined in Appendix I ․ Process sludge ․ Waste agricultural chemicals Generated from Manufac./Sale of agricultural chemicals

• 2. Corrosive waste

․ Waste acids (pH≤2.0) Liquid state ․ Waste bases (pH≥12.0) * NaOH, KOH included

• 3. Hazardous containing

waste ․ Slag (ExcludedblastfurnaceslagusingIronOres) Containing in Appendix 1 ․ Dust (Collected Air Pollution Device) * Excluded generated from incineration facility ․Waste foundry san and waste sand blast ․Waste refractory, Ceramics with glaze ․ Incineration ash ․Stabilization/Solidification solid (disposal) waste ․Waste catalysts ․Waste adsorbents/Absorbents ․Waste earth and sand for animal oil purification

• 4. WasteSolvent

․halogens Defined in Appendix I ․Other waste solvents Excludedhalogens

4 (≥ 1 item) Or 3 (≥ 2 items)

Accident Type Explosion Release

Waste (Facility, Contaminant)

Waste Management

• Ind. Safety and

Health Law

NFPA code

Waste Classification

NFPA Code & pH Score Check

General Waste Designated Waste 3 (≥ 1 item) + Special Hzd

• r ∑(NFPA+pH) ≥ 9)

YES NO

Consideration of Current Laws or Regulations without Q

NO

4 (≥ 1 item

• r 3 (≥ 2 items)

Inflammability Inflammability by MSDS or NFPA Class Waste (Facility, Contaminant) g Waste Management

• Ind. Safety and

Health Law

NFPA code

NFPA Code & pH Score Check General Waste C/D Designated Waste C/D

3 (≥ 1 item) + Special Hzd

• r ∑(NFPA+pH) ≥ 9)

YES

NO Classification/Disposal (C/D) by Currents laws YES Current Laws Current Laws YES NO

Consideration of Current Laws or Regulations with Inflammability

WASTE (Chemical & Facility) Designated Waste General Waste

Acid pH ≤ 2.0 Base pH ≥ 12.5 Flammability NFPA ≥ 3 Reactivity (Instability) NFPA ≥ 3 Health Hazard NFPA ≥ 3

∑NFPA ≥ 6 ∑NFPA ≥ 5 & 1SH* ∑NFPA ≥ 4 & 2SH* Radioactive Biohazard

YES YES YES YES YES NO NO NO NO NO *SH : Specific Hazard OX : Oxidizer W : Use NO WATER COR : Corrosive Specified in Waste Control Act NO YES

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