Transcript PowerPoint Sunusu

RISKS,
CONTROL MEASURES,
APPLICATIONS
IN CHEMICAL INDUSTRY
Content
1.
Definitions
2.
Hazards and Risks Arising from Chemicals
3.
Risk Assesment of Chemicals
- Labelling of Chemicals
- Material Safety Data Sheets
4. Principles for Eliminating or Reducing Risks
5. Application of the Principles for Prevention
6.
Safe Storage of Chemicals
7.
Implementing Regulations on EU
1. Definitions
Chemical agent: Means any chemical element, compound or a
mixture of them, as it occurs in the natural state or as produced,
used or released by any work activity or come about as waste or
produced unintentionally.
Implementing Regulation on the Protection of the Health and Safety
Measures from the Risks Related to Chemical Agents at Work (based on the
Directive 1998/24/EC)
Definitions
Chemical Agents



Any substance that has one or more of characteristics that are toxic for
reproduction and dangerous for the environment like being explosive,
oxidizing, easily flammable, flammable, toxic, very toxic, hazardous,
corrosive, irritating, allergic, carcinogen, mutagen.
Any chemical agent that is not mentioned in the classifications above but
due to its chemical, physico-chemical, or toxicological properties, and the
way it is used or present in the workplace, present a risk to the safety and
health of workers.
Chemical agents with established occupational exposure limit value.
Definitions
Hazard is the intrinsic capacity of a chemical agent to cause harm.
Risk is the likelihood that the potential for harm will be attained under the
conditions of use and/or exposure.
Exposure to chemical agents is any work situation in which a chemical agent
is present and the worker comes into contact with this agent, normally
through the skin or via inhalation.
Use of Chemical Agents in the Last 5 Years (in EU)
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Construction and associated activities (carpentry, painting, water, gas and
electrical installations, etc.);
Professional cleaning,
Hospitals,
Waste –processing industry,
Agriculture,
Metalworking and mechanical industries,
Mechanical workshops,
Printing works,
Chemists’ shops,
Laboratories,
Restoration of works of art,
Hairdressing salons.
Classifications according to 67/548/EEC
(published in December 2008 in Official Paper in
Turkey)
E Explosive
T+ Highly toxic
C Corrosive
O Oxidising
T Toxic
Xi Irritant
F+ Highly
flammable
Xn Harmful
F
Flammable
N Nature
polluting
Classifications according to Globally Harmonized
System(GHS)
Compressed gas
Toxic gas
Flammable solid
Spontaneously
combustible
Organic Peroxides
Toxic
Flammable gas
Dangerous
when wet
Flammable Liquid
Oxidising agent
Corrosive
Globally Harmonized System(GHS) Overview
– The UN-developed system „GHS“ standarts for
"Globally Harmonized System of Classification and Labeling of Chemicals"
– With GHS, globally harmonized criteria have been created for the classification
and labeling of chemicals. GHS wants to ensure internationally comparable high
standards for health and consumer protection, occupational health and safety,
and environmental protection.
– GHS regulates ...
• criteria for the classification of physical, toxicological, and environmental
relevant properties ...
• classification and labeling ...
• harmonized hazard communication ...
(e.g. harmonized label statements and harmonized safety data sheets)
... of chemicals.
GHS Overview
– GHS affects manufacturers, suppliers, and users of chemicals
– The global implementation of GHS should take place during 2008.
The registration phase of REACH, the uniform chemical law applicable within
the EU, also begins in 2008.
– Because of the numerous interconnections between GHS and REACH,
the European Commission has scheduled the implementation of
the two regulations to follow each another in quick succession.
– The implementation of GHS is progressing at different paces around the
world. In many Asian countries, for example, GHS has already been
introduced.
What must be done?
The conversion to GHS has significant effects on the handling of chemicals.
– All products have to be checked to be in line with the requirements of GHS.
– Within the transition periods,
• labeling shall be adapted to the new requirements.
• safety data sheets shall be correspondingly changed.
– All substances which meet the criteria for classification as hazardous and
are placed on the market shall be notified to the European Chemicals Agency
(ECHA) for inclusion in the classification and labeling inventory.
The Timeline
– The implementation timeline provides the following critical milestones:
• On January 1, 2009, GHS enters into force
• By December 1, 2010, all substances shall be classified and labeled
in accordance with GHS criteria
• By June 1, 2015, all mixtures shall be classified and labeled
in accordance with GHS criteria.
The Timeline
– The implementation timeline provides the following critical milestones:
• On January 1, 2009, GHS enters into force
• By December 1, 2010, all substances shall be classified and labeled
in accordance with GHS criteria
• By June 1, 2015, all mixtures shall be classified and labeled
in accordance with GHS criteria.
What essential changes does GHS involve?
– GHS introduces globally harmonized criteria for the classification of physical,
toxicological, and environmental relevant properties.
– GHS establishes globally harmonized criteria for hazard communication. In the
overview, this relates to the introduction of new or modified:
• hazard classes,
• hazard categories,
• hazard pictograms,
• signal words,
• hazard statements,
• precautionary statements.
– GHS offers the opportunity to bring product safety to a high level all over the
world.
GHS will thus contribute to improving measures for protecting human health
and the environment on a global scale.
New Labeling Elements
Signal word
The signal word on the label gives information
about the relative hazard level of a substance
or mixture and alerts the reader to a
potential hazard.
Hazard pictogram
• Square set on a point,
• Red border,
• White background,
• Black symbols.
Danger
Warning
New pictograms – the most striking GHS feature
Physical Hazards
Health Hazards
Env. hazards
Classifications according to GHS
Compressed gas
Toxic gas
Flammable solid
Spontaneously
combustible
Organic Peroxides
Toxic
Flammable gas
Dangerous
when wet
Flammable Liquid
Oxidising agent
Corrosive
Hazard statements, definition and coding
A hazard statement is a phrase, assigned to a hazard class and category
that describes the nature / intrinsic property of a hazardous product as well
as the hazard level.
Hazard statement group
2 Physical hazards
3 hazards
4 al hazards
Hazard statement
H300 – Fatal if swallowed
Sequence in the group
Precautionary statements, definition and coding
A hazard statement is a phrase, assigned to a hazard class and category
that describes the nature / intrinsic property of a hazardous product as well
as the hazard level.
Precautionary statement group
2 Prevention
3 Response
4 Storage
5 Disposal
Precautionary statement
P 380 – Evacuate area
Sequence in the group
The labeling must be adapted to the new regulations
2. The Hazard Associated with Chemicals
Chemical agents can cause harm;
1. either directly,
2. or by producing some form of energy (such as fire or explosion).
The Hazard Associated with Chemicals
For the 1st case;

Harm can become apparent rapidly or even immediately after contact
(Acute Effect)

Or appear in the long term due to repeated exposure over time
(Chronic Effect)

If the harm is apparent at the point of the contact of chemical and the
body

Local Effect
Or if may appear following a process of absorption and
distribution through the body
Systemic Effect
The Harm Caused by Chemicals
For the 2nd case;
 The harm is caused by the energy produced by the fire or explosion
of chemical agents.
 Explosions occur when a sudden oxidation or decomposition
reaction occurs producing a temperature and pressure rise or both
simultaneously. .
The Hazard Posed by Chemicals
Chemical agents present in workplace may pose risks to health and safety on account of;
1. Their hazardous properties (physico-chemical or toxicological) (e.g. explosive or
sensitiser)
2.
The temperature or pressure at which they occur in the workplace (e.g. water vapor at
150°C)
3.
Their capacity to displace the atmospheric oxygen from the workplace (e.g.
pressurized inert gas)
4.
The manner in which they are present in the workplace (e.g. inert solid in the form of
a breathable powder)
3. Risk Assesment of Chemicals
Risks to be assessed;
1.
The risk of fire and/or explosion,
2.
Risk generated due to the hazardous chemical reactions which may
affect the health and safety of workers,
3.
Risk due to inhalation,
4.
Risk due to absorption through the skin,
5.
Risk due to contact with skin or eyes,
6.
Risk due to ingestion,
To Assess the Risks of Chemicals

To determine the risks of a chemical agent; the hazardous properties of
these chemicals and the way in which they are present and are used must
be known.

To assess the risks first be informed about the hazardous properties of
chemicals.
(Directive 2000/39/EC)
 Labelling
 Material Safety Data Sheets (MSDS)
 Occupational Exposure Limit Values and Biological Limit Values
Labelling
Material Safety Data Sheets (MSDS)
1. Identification of
substance/preparation and company
2. Composition/information of
ingredients
3. Hazard identification
4. First-aid measures
5. Firefighting measures
6. Accidential spillage measures
7. Handling and storage
8. Exposure controls/personal
protection
9. Physical/Chemical properties
10. Stability and reactivity
11. Toxicological information
12. Ecological information
13. Disposal considerations
14. Transport information
15. Regulatory information
16. Other information
Application of MSDS
 General Information
Chemical Composition
Physico-chemical Properties
Section 2
Section 9
 Use
Recommended uses and restrictions
Handling and Storage
User Protection
Exposure Limit Values
Section 16
Section 7 and 15
Section 8
Section 8 and 15
Application of MSDS
 Hazards
Safety: Flammability, explosiveness, reactivity
Health: Toxicity
Environment: Ecotoxicity
Section 3,9,10
Section 3 and 11
Section 3 and 12
 Emergencies
First aid
Fire
Leaks/releases
Section 4
Section 5
Section 6
Occupational Exposure Limit Value
 Specific reference parameters used in assessing risks due to exposure
to chemical agents in the workplace.
 All EU Member States must have their own national list of exposure
limits and biological limits in accordcance with Directive 98/24/EC.
 According to Community Legislation (Directive 98/24/EC), any
substance which has an exposure limit value must be regarded as
hazardous substance.
Risks Arising from Hazardous Chemicals
Risks Arising from Hazardous Chemicals
General Principles for Eliminating/Reducing Risks
1. Design and organisation of systems of work at the workplace.
2. Provision of suitable equipment for work with chemical agents and
maintenance procedures which ensure the health and safety of workers at
work.
3. Reducing to a minimum the number of workers exposed or likely to be
exposed.
4. Reducing to a minimum the duration and intensity of exposure.
General Principles for Eliminating/Reducing Risks
5. Appropriate hygiene measures.
6. Reducing the quantity of chemical agents present at the workplace to the
minimum required for the type of work concerned.
7. Suitable working procedures including arrangements for the safe handling,
storage and transport within the workplace of hazardous chemical agents
and waste containing such chemical agents.
Application of the Principles for Prevention
Specific Prevention Measures & Prioritisation
Action Diagram for Risk Assesment and Resulting Actions
An Example: Substitution of the Chemical Agent
• In accordance with the Directive 98/24/EC, substitution of hazardous
chemical agent shall be preferred as a specific measure for eliminating or
reducing the chemical risk.
• Example: In a process, benzene is being used, which has a IARC
classification of 1, carcinogenic to humans. Occupational Hygienist want to
substitute benzene with toluene.
• Before the substitution the hazards of toluene and benzene should be
evaluated in order to decide whether toluene is less hazardous than
benzene.
• In order to assess the substitution, first we examine the risk phrases of
benzene and toluene;
R-phrases of benzene: R11, R23, R24,R25, R45, R48
R-phrases of toluene: R11, R20
Risk Level
Acute Health
Chronic
Fire and
Exposure
Hazards
Risk
Health Risk
Explosion Risk
Potential
Associated
with Process
Very High
High
Medium
Low
Negligible
Benzen (R45)
Benzen (R25)
Benzen
Benzen
Toluen (R11)
(VP.101 hPa)
Toluen
Toluen
Benzen
(R20)
(VP.29 hPa)
Toluen
• napo\napo-sgh-03-flammable-eng.avi
6. Safe Storage of Chemicals
Main Principle: In terms of prevention, the main measure is to maintain the
hazardous chemical stocks at the lowest possible level or to change
chemicals used with less dangerous ones. Then maintain;
 Safe storage area away form process area or other hazardous areas,
 Avoid the combined storage of incompatible or highly reactive chemicals,
 Provide secure containers (sufficient physical resistance, automatic closure,
appropriate for the type and quantity of chemical stored etc.).
Safe Storage of Chemicals
 To a large extent, how the chemical groups are divided and assigned,
will depend largely upon the amount of space available.
 The risk associated with incompatible chemicals coming into contact
must be avoided wherever chemicals are handled or stored.
 The common features uniting all these plans is the separation of
incompatible materials.
The ten most commonly cited groups are:
- flammables, oxidants, reducers, concentrated acids, concentrated
bases, water reactives, extreme toxics, peroxide formers, pyrophorics
and gas cylinders.
Examples of;
Incompatible Agents
 Oxidising Agents with; inflammable substances, nitrides, hydrides,
sulphides, alkylmetals
 Reducing Agents with: nitrates, chlorates, oxides, peroxides, fluoride
 Strong Acids with Strong Bases
 Sulphuric acid with: cellulose, perchloric acid, potassium
permanganate, chlorate
Examples of;
Unstable Substances
 Products that may decompose when stored long periods: alkaline
anhydrides
 Substances that readily peroxidise: allylic compounds, styrene
 Compounds that react violently on contact with air: phosphides, hydrides
 Monomers that polymerise rapidly: styrene, acrylonitrile
Safe Storage of Chemicals
 Violent reactions occur when the following chemicals from different
Storage Groups are mixed:
– Corrosives + Flammables = Explosion/Fire
– Corrosive + Poisons = Poison Gas (Toxic Gas)
– Flammables + Oxidizers = Explosion/Fire
– Acids + Bases = Corrosive Fumes/Heat
Highly flammable
Explosive
Toxic
Oxidising
Harmful
+
-
-
-
+
-
+
-
-
-
-
-
+
-
+
-
-
-
+
0
+
-
+
0
+
Safe Storage of Chemicals
Basic Storage Requirements:
 Label storage areas according to the type of chemical family or hazard
classification found there,
 Inspect storage areas at least annually,
Keep aisles, hallways, doorways, exits, and entryways clear,
 Keep storage areas well lit, appropriately ventilated, and at a consistent,
cool temperature.
Safe Storage of Chemicals
Basic Storage Requirements (Cont’d)
 Eliminate ignition sources such as open flames, heat sources, or direct
sunlight.
 Keep emergency equipment such as fire extinguishers handy and in good
working order.
 Confine chemical storage areas so that leaks or spills are controlled.
Prevent chemicals from running down sink, floor, or storm water drains.
Clean up spills and drips immediately.
Safe Storage of Chemicals
Storage Don’ts !
 Don’t store chemicals in a sink or fume hood, except for certain toxic gases
that are so dangerous they can only be stored in a gas cabinet or fume
hood.
 Don’t store chemicals on dirt or grass, near a creek or storm drain
entrance, where they could contaminate the environment.
 Don’t store chemicals on the floor, window ledges, or balconies.
Safe Storage of Chemicals
To avoid explosion;
 Store two incompatible chemicals at least 3 m. apart.
 Where the goods could react violently, store them at least 5 m. apart.
 Consider storing some chemicals especially unstable chemicals in separate
fire rated enclosures or separate buildings with appropriate fire
suppression equipment.
Implementing Regulations on the Protection of the
Risks Related to Chemical Agents
Identification of HCAs (Hazard Chemical Agents)
•
Council Directive 67/548/EEC, as amended and adapted to technical progress, on
the approximation of laws, regulations and administrative provisions relating to the
classification, packaging and labelling substances;
•
Directive 1999/45/EC of the European Parliament and of the Council, as
subsequently adapted to technical progress, relating to the classifcation, packaging
and labelling of dangerous preparations;
•
Commission Directive 91/155/EEC , as amended, by Directive 2001/58/EC defining
and laying down the detailed arrangements for the system of specific information
relating to the dangerous preparations and substances(MSDS)
Implementing Regulations on the Protection of the
Health and Safety Measures from the Risks Related to
Chemical Agents at Work
Chemical Safety
•Council Directive 96/82/EC on the control of major-accident hazards involving
dangerous
substances,
and
subsequent
Commission
decisions
on
its
application;(SEVESO-II)
•Directive 94/9/EC of the European Parliament and the Council on the
approximation of the laws of the Member States concerning equipment and
protective systems intended for use in potentially explosive atmospheres;
•Directive 1999/92/EC on minimum requirements for improving the safety and
health protection of workers potentionally at risk from explosive atmospheres.
Implementing Regulations on the Protection of the
Health and Safety Measures from the Risks Related to
Chemical Agents at Work
Work with particular HCAs
•Directive 2003/18/EC of the European Parliament and of the Council Directive
83/477/EEC on the protection of workers from the risks related to exposure to
asbestos at work,
• Council Directive 98/24/EC on the protection of the health and safety of workers
from the risks related to chemical agents at work,
•Council Directive 90/394/EC, as amended (Directive 97/42/EC and Directive
1999/38/EC), on the protection of workers from the risks related to exposure to
carcinogens at work.
Conclusions
• All substances must be stored in securely closed containers
designed for the purpose
• All substances must be clearly labelled in ordered to
determine the hazards on the material
• Read always MSDS in order to acquiring understanding of
all hazardous properties of a specific substance
• Careful analysis of substance properties will curtail adverse
reactions involving intentional mixing of chemicals or
malfunction at storing
References
•
Articles 3, 4, 5 and 6, and Annex II, Section I, of Directive 98/24/EC
•
European Commission, Employment, Social Affairs and Equal Opportunities, Particle
Guidelines of a Non-binding Nature on the protection of the Health and Safety of Workers
from the Risks Related to Chemical Agents at Work , June 2005
•
Safe Storage of Hazadous Chemicals, University of California, Berkeley, Office of
Environment, Health & Safety.
•
İzmir Yüksek Teknoloji Enstitüsü, Mühendislik Fakültesi, Kimya Mühendisliği, Kimyasal
Hijyen Planı, 2007.
•
Finnish Institute of Occupational Health, Pirjo Irmeli Korhonen, 2010
•
Arme İstisnai Eğitim ve Danışmanlık Hiz. Ltd. Şti, Endüstriyel Tesislerde Tehlikeli Kimyasal
Yönetiminin İlkeleri, Adana, 2007.
•
Pirjo I Korhonen, Dangerous interactions between stored chemicals, INT MARKT IND/EXP
34794, 2010, Ankara