: Development of Selection Criteria as Designated (Special ...

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 DiffusionHazardous chem. Leaks

Environ. Pollution

Suffocation by Combustion Gases

Radiative HeatBuilding 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/)

0

10.000

20.000

30.000

40.000

50.000

60.000

2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Tota

l Em

issi

ons

(Ton

e/yr

)

Year

No.

of C

hem

ical

Acc

iden

ts

Year

Number of Chemical Accidents in Korea

Damage from Chemical Accidents in Korea

Year Classification Casualty and cost

2012human damage

death 11 people

injury 47 people

material damage 55.4 M US$

2013human damage

death 11 people

injury 70 people


2014human damage

death 4 people

injury 234 people


2015human damage

death 9 people

injury 97 people


2016human damage

death 5 people

injury 120 people


No.

of C

hem

ical

Acc

iden

ts

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 A

ccid

ents

MiscellaneousManufacturing

In use

Storage

TransportSale

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 of 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 acidsame as TATP explosives raw materials

(triacetone triperoxide, primary high explosive)

Pipe corrosion/abrasion

Inappropriate Handling


Inappropriate Loading Lack of driver’s knowledge Difficulty transport tracking

Dangerous Transport Habits


Excessive/Open/Untided Loading

Dangerous/ExplosiveChemicals/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)

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<DQ<D/2

Classification by MSDS Scores (Designated vs. General)

Q≧D/2

Yes

Yes Yes

Yes

N0N0

N0 N0

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

건강

위험성반응성

화재

위험성

특수

위험성

4

2

0

₩OX

National Fire Protection Association : NFPA

scorecheck

NFPAcode

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 0

▪ NFPA Code Class +pH

▪ Korean regulation: Designated Waste STD (pH ≧ 12.5, pH ≦ 2)

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

scorecheck

NFPA codeand 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)

scorecheck

NFPA codeand 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 YN 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 0 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 0 3 ㅇ 3

9 Arsine 4 4 2 ㅇ

10 benzene 2 3 0 ㅇ 3

11 benzyl chloride 3 2 1 ㅇ 3

12 butylamine 3 3 0 ㅇ

13 carbon disulfide 3 4 0 ㅇ

14 carbon monoxide 4 4 2 ㅇ

15 chlorine 3 0 0 OX ㅇ

16 chlorine dioxide 3 0 4 OX ㅇ

17 chlorosulfonic acid 4 0 2 \,OX ㅇ

18 Cyanogen chloride 4 0 2 ㅇ

19 diborane 3 2 0 ㅇ 3

20 ethyl acetate 4 4 3 ㅇ

Accident causing material Health Fire Reactivity Specific Designated pH Condition (more than)

21ethyl methyl ketone perox

ide2 4 0 ㅇ

22 ethylene oxide 3 4 3 ㅇ

23 ethylenediamine 3 3 0 ㅇ

24 ethyleneimine 4 3 3 ㅇ

25 fluorine 4 0 4 \,OX ㅇ

26 formaldehyde 3 4 0 ㅇ

27 formic acid 3 2 1 ㅇ 3

28 Hexamine 1 1 0 ㅇ 4

29 hydrogen chloride 3 0 1 ㅇ 3

30 hydrogen cyanide 4 4 1 ㅇ

31 hydrogen flouride 4 0 1 ㅇ

32 hydrogen peroxide 3 0 2 OX ㅇ

33 hydrogen sulfide 4 4 0 ㅇ

34 isophorone diisocyanate 2 1 1 \ ㅇ 3

35 meta-cresol

36 methanol 1 3 0 ㅇ 3

37 methyl acrylate 3 3 2 ㅇ

38 methyl chloride 2 4 0 ㅇ

39 methyl vinyl ketone 1 3 0 ㅇ 3

40 methylamine 2 2 4 OX ㅇ

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


41 methylethylketone 4 3 2 ㅇ

42 methylhydrazine 4 3 2 ㅇ

43 nitric acid 3 4 0 ㅇ

44 Nitric oxide 4 0 1 OX ㅇ

45 Nitrobenzene 3 0 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 0 COR ㅇ

50 phosphorus oxuchloride 4 0 1 ㅇ

51 phosphorus trichloride 4 4 2 ㅇ

52 p-nitrotoluene 4 0 2 \ ㅇ

53 Potassium chlorate 4 0 2 \ ㅇ

54 Potassium perchlorate 2 3 0 OX ㅇ

55 Potassium perchlorate 1 0 0 OX ㅇ 3


56 Potassium permangante 1 0 1 OX ㅇ 3

57 propylene oxide 2 0 0 OX ㅇ 3

58 Sarin 3 4 2 ㅇ

59 sodium 3 3 2 \ ㅇ

60 Sodium chlorate 2 0 3 OX ㅇ

61 sodium cyanide 4 0 0 ㅇ

62 Sodium nitrate 1 0 0 OX ㅇ 3

63 sulfuric acid 3 0 2 \ ㅇ

64 toluene 2 3 0 ㅇ 3

65 toluene-2, 4-diisocyanate 3 1 2 ㅇ 3

66 triethylamine 3 3 0 ㅇ

67 trimethylamine 3 4 0 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 ReleaseQ = Contaminant QuantityD = 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

GeneralDesignated

NONOYES

YES

∑( p ) )3 (≥ 1 item) + Special Hz

∑(NFPA+pH) ≥ 9)

YES

NOYES NO

Regulations of Waste Management LawLarge Category Medium Category Small Category Memo

1. Specific site waste

․Waste Polymers․Waste resin

ExcludeSolidstate․Waste rubber

․Sludge : Moisture [(<95%or Solid content (<5%)]

․Wastewater sludgeDefined in Appendix I

․ Process sludge

․ Waste agricultural chemicals Generated from Manufac./Sale ofagricultural chemicals

2. Corrosive waste․ Waste acids (pH≤2.0)

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

3. Hazardous containingwaste

․ 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 ManagementInd. Safety and Health Law NFPA code

Waste Classification

NFPA Code & pH Score Check

General WasteDesignated Waste

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

YES NO

Consideration of Current Laws or Regulations without Q

NO

4 (≥ 1 item or 3 (≥ 2 items)

Inflammability

Inflammability by MSDS or NFPA Class

Waste (Facility, Contaminant)

gWaste

ManagementInd. Safety and

Health Law NFPA code

NFPA Code & pH Score Check

General Waste C/D

Designated Waste C/D

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

YES

NOClassification/Disposal (C/D) by Currents laws

YESCurrent LawsCurrent Laws

YES

NO

Consideration of Current Laws or Regulations with Inflammability

WASTE (Chemical & Facility)

Designated Waste General Waste

Acid pH ≤ 2.0Base pH ≥ 12.5

FlammabilityNFPA ≥ 3

Reactivity(Instability)NFPA ≥ 3

Health HazardNFPA ≥ 3

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

RadioactiveBiohazard

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

35

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Natural Beauty of Ulsan, The largest Industrial City in Korea

: Development of Selection Criteria as Designated (Special ...

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