REFRIGERANTS AND
ENVIRONMENT
MARPOL 73/78
• Annexe VI contains Regulations for the
Prevention of Air Pollution from Ships.
• Divided into 3 chapters
• Chapter I -General having 4 Regulations
(1-4)
• Chapter II- Survey Certification of
Means of Control having 7 Regulations
(5-11)
• Chapter III- Requirements for Control of
Emission from Ships having 8
Regulations (12-19)
MARPOL 73/78 Contd.
CHAPTER I
• Regulation 1-Applications
• Regulation 2- Definitions
• Regulation 3- General Exceptions
• Regulation 4- Equivalents
MARPOL 73/78 Contd.
CHAPTER II
• Regulation 5-Surveys and
Inspections
• Regulation 6-Issue of International
Air Pollution Prevention Certificate
• Regulation 7-Issue of Certificate by
another Government.
• Regulation 8-Form of Certificate
MARPOL 73/78 Contd.
CHAPTER II Contd.
• Regulation 9-Duration and Validity of
Certificate
• Regulation 10-Port State Control on
operational requirements
• Regulation 11-Detection of violations and
enforcement
MARPOL 73/78 Contd.
CHAPTER III
• Regulation 12- Ozone Depleting
Substances
• Regulation 13- Nitrogen Oxides (NOx)
• Regulation 14- Sulphur Oxides (SOx)
• Regulation 15-Volatile Organic
Compounds
MARPOL 73/78 Contd.
CHAPTER III Contd.
• Regulation 16- Shipboard Incineration
• Regulation 17-Reception Facilities
• Regulation 18- Fuel Oil Quality
• Regulation 19- Requirements for
platforms and drilling rigs
MARPOL 73/78 Contd.
Regulation 12 deals with Ozone
Depleting Substances
• Definition: Ozone Depleting
Substances means controlled
substances defined in Paragraph 4 of
article 1 of the Montreal Protocol on
Substances that Deplete the Ozone
Layer, 1987.
MARPOL 73/78 Contd.
Definition Contd.
The following Halons are listed
• Halon 1211
Bromochlorofluoromethane
• Halon 1301 Bromotrifluoromethane
• Halon 2402 1,2-Dibromo-1,1,2,2tetrafluoro ethane (also known as
Halon 114B2)
MARPOL 73/78 Contd.
Definition Contd.
The following Refrigerants are listed
• CFC-11 Trichlorofluouromethane
• CFC-12 Dichlorodifluouromethane
• CFC-113 1,1,2-Trichloro-1,2,2trifluoroethane
• CFC-114 1,2-Dichloro-1,1,2,2tetrafluoroethane
• CFC-115 Chloropentafluoroethane
MARPOL 73/78 Contd.
Regulation 12 is about Ozone Depleting
Substances
• Subject to the provisions of Regulation 3,
any deliberate emissions of ozone
depleting substances shall be prohibited.
• Deliberate emissions include emissions in
the course of maintaining, servicing,
repairing or disposing of systems or
equipment except that deliberate
emissions do not include minimal releases
associated with the recapture or recycling
MARPOL 73/78 Contd.
Regulation 12 Contd.
• Emissions arising from leakage of an
ODS, whether or not the leaks are
deliberate, may be regulated by
Parties to the Protocol of 1997.
• New installations which contain
ODSs shall be prohibited on all
ships, except that new installations
containing hydrochlorofluoro
carbons (HCFCs) are permitted
until 1 January 2020.
MARPOL 73/78 Contd.
Regulation 12 Contd.
• The substances referred to in this
regulation and equipments
containing such substances, shall be
delivered to appropriate reception
facilities when removed from ships.
WHAT ARE THE VARIOUS
SUBSTANCES THAT CAN
CAUSE OZONE DEPLETION?
CFCs and HCFCs used in following
applications:
• Air Conditioning Fire fighting
• Refrigeration
Adhesives
• Pesticides
Aerosols
• Plastic Foams
Chemical feedstock
etc.
• Solvents
VARIOUS
REFRIGERANTS
• CFCs- R-12,R-11, R-113, R-114,
R-115 etc.
• HCFCs- R-22, R-123, R-124 etc.
• HFCs- R-134a, R-125, R-148a,
R-152a etc.
VARIOUS REFRIGERANTS
Contd.
• Freon is Dupont’s trademark for its
fluorocarbon refrigerants.
• All Refrigerants have one Carbon
atom as their origin is from Methane
(CH4) or Ethane C2H6 where one or 2
Hydrogen atoms have been replaced
with Chlorine, Fluorine or Bromine.
VARIOUS REFRIGERANTS
Contd.
Methane Derived Refrigerants
• R No. viz. R-11, R-12, R-22 etc.
First figure shows the number of
Hydrogen atoms plus one.
Second figure shows the number of
Fluorine atoms.
The total number of Hydrogen and other
replacement atoms should be 4
VARIOUS REFRIGERANTS
Contd.
Methane Derived Refrigerants Contd.
• R-11: CCl3F CFC
• R-13: CClF3 CFC
• R-22: CHClF2 HCFC
• R-12:CCl2F2 DichlorodifluoroMethane
CFC
• R 113: CCl2F/CClF2
• R 501:Mixture 75%-R22 and 25%-R12
• R 502:Mixture 75%-R12 and 25%-R22
VARIOUS REFRIGERANTS
Contd.
Ethane Derived Refrigerants
• R No: viz. R 113, R 114, R 115 etc.
First Figure shows number
of Carbon atoms minus 1
Second figure shows number of
Hydrogen atoms plus 1
Third figure shows number of
Fluorine atoms.
VARIOUS REFRIGERANTS
Contd.
Ethane Derived Refrigerants Contd.
• R-113- 1,1,2 Trichloro
1,2,2 Trifluoro ethane
• R-114- 1,2 Dichloro
1,1,2,2 Tetrafluoroethane
• R-115- Chloropentafluoroethane
• R-134a C2H2F4 Tetra Fluoro Ethane (a
stands for isomer- same chemical
composition but different atomic
arrangement)
KEY REFRIGERANT
CHARACTERISTICS
AFFECTING
ENVIRONMENT
•
•
•
•
Ozone Depletion Potential ODP
Global Warming Potential GWP
Chlorine leading Potential
Atmospheric Life (years)
MONTREAL PROTOCOL
• Signed on September 16, 1987 under
the auspecies of IMO.
• Seeks to inhibit production,
consumption and trade of ozone
depleting compounds.
• Also distinguishes between
developed countries with higher
consumption and developing
countries with lower countries.
UNEP CONFERENCE
• Dated 25 November 1992.
• New CFCs will be stopped production
after 1995 and HFCs after 2020.
ENVIRONMENT
Definition
The conditions and
influences of the place in which
an organism lives.
In layman’s terms, it is known
as Surroundings.
ECOLOGY
Definition
The Study of
relationship between living
organisms and their
Environment.
ATMOSPHERE
Definition
The layer of gas surrounding
a planet or a star.
• Earth’s Atmosphere Composition
Oxygen: 21% Nitrogen: 78%
CO2, H2, Argon and other Gases:
1%
ATMOSPHERE Contd.
Earth’s Atmosphere consists of the
following layers
TROSPHERE Closest to Earth’s
surface upto 14 kms height
STRATOSPHERE upto 44 km height
IONOSPHERE consisting of
MESOSPHERE upto 80 km
height
and THERMOSPHERE
above 80 km
height
• Each of these layers is seperated by
TROPOPAUSE, STRATOPAUSE,AND
OZONE
• Formed by the action of Ultra Violet
Light from the sun on Oxygen in the
atmosphere.
• Boiling Point is -112 deg C.
• Chemically very active, can readily react
with any other chemical atoms present
closeby.
• It has a great affinity to Chlorine and
can engage in a catalytic reaction in
which each chlorine fragment can
destroy upto 100000 ozone molecules
before the chemical processes remove the
OZONE LAYER
• Present in Stratosphere at heights 11 km
to 50 km above Earth’s surface.
Stratosphere temperature ranges from 56 deg C to -2 deg C.
• Most concentrated at height of 22 km.
• Highest concentration of about 10 ppm.
• It accounts for less than one-millionth
part of Earth’s Atmosphere.
• But it is of vital importance for Earth’s
life-form.
OZONE LAYER Contd.
• The ozone layer is not constantly thick all
over the earth’s surface.
• Ozone Molecules are formed over the
tropics and are delivered along with the
chlorine to the Arctic and Antarctic with
atmospheric Motion.
• A circulation pattern called Antarctic
and Acrtic Polar Vortex traps the ozone
near the poles for several months.
OZONE LAYER Contd.
IMPORTANCE OF OZONE LAYER
• It absorbs the UV-B rays while allowing
the heat generating infra-red rays to
reach the earth. This heat is lifesustaining on the planet keeeping the
temperatures of planet at desired levels.
• It influences the weather by stabilizing
the stratosphere which acts as a cap to
the turbulent weather system in the
troposphere.
FORMATION OF OZONE
LAYER
• Ultra Violet Radiation below 190 nm is
removed before it reaches Stratosphere
by atmospheric nitrogen and oxygen.
• U V Radiation between 190 nm and 340
nm is removed in Stratosphere by the
reaction O2 + hV = O + O*
• There is continuous cyclic formation and
destruction of ozone due to foll: reactions
O + O* =O3 + M*; O3 + hV = O3 + O
O3 + O2 = 2 O2
•
FORMATION OF OZONE
LAYER
Contd.
The absorption of UVRadiation in
Stratosphere prevents virtually all
radiation below 290 nm and mostly
between 290 nm and 320 nm from
reaching the earth.
• Above the Stratosphere, the density of
gases is so low that O2 atoms rarely find
other molecules to collide with; so ozone
is not found in abundance.
• Below the ozone layer, too little solar
radiation penetrates to allow appreciable
DEPLETION OF OZONE
LAYER Contd.
Process
• Chlorine in Stratosphere becomes
trapped in so called reservoir compounds
such as Hydrogen Chloride and Chlorine
Nitrate which themselves do not destroy
Ozone.
• Once Stratosphere becomes cold enough
to freeze closed particles, ice crystals
provide surfaces on which reactions can
occur.
DEPLETION OF OZONE
LAYER
Contd.
Contd.
Process
• Chlorine Nitrate ClONO2 reacts with
Hydrochloric Acid present on ice surface,
producing molecular chlorine and Nitric
Acid.
• Nitric Acid remains bonded to the ice
and molecular Chlorine is quickly broken
down into Atomic Chlorine which reacts
with Ozone destroying it through
production of chlorine Monoxide and
Molecular Oxygen.
DEPLETION OF OZONE
LAYER Contd.
Process Contd.
• Chlorine Monoxide undergoes further
reactions that reform a chlorine atom
which is free to destroy another Ozone
molecule.
• The Ozone depleted is transported from
the polar regions to lower latitudes
through wind in the late spring when
antarctic Vortex breaks up.
DEPLETION OF OZONE
LAYER Contd.
Process Contd.
• Ozone depletion process is accelerated
during presence of sunlight and low
temperatures.
DEPLETION OF OZONE
LAYER Contd.
Where does the Chlorine come from?
• CFCs are one particular class of Refrigerants
and Fire Extinguishing Mediums containing
Chlorine and Fluorine Atoms. Ex. R-12, R-11.
• They are chemically very stable and remain
unchanged in the lower atmospheric layer
(Troposphere).
• Upon reaching Stratosphere, they encounter
high energy Ultra Violet light which breaks
them releasing Chlorine atoms.
DEPLETION OF OZONE
LAYER Contd.
Chlorine Levels in Stratosphere
• 1970 - 1.2 parts per billion
• 1985 - 3.0 parts per billion
• 2050 projected - 8.2 parts per billion
1 Chlorine Atom can destroy upto 100000
ozone molecules before the chemical
processes remove the Chlorine from the
Atmosphere.
DEPLETION OF OZONE
LAYER Contd.
• Ozone Hole keeps forming over
Antarctica during certain months of the
year.
• The lowest ozone levels were recorded
over South Pole in the first 2 weeks of
October 1987.
DEPLETION OF OZONE
LAYER Contd.
What happens if the atmospheric Ozone
Layer gets depleted?
• Ultra Violet rays from sunlight can reach
the Earth
can damage human immune system,
can cause cataracts,
increase incidence of skin cancer.
• Every 1% depletion of Stratospheric
Ozone, results in 2% rise in skin cancer.
• In USA, 3000000 to 4000000 new cases of
skin cancer are reported every year.
DEPLETION OF OZONE
LAYER Contd.
• Effects on Plants: Reduced leaf size,
stunted growth, poor seed quality,
susceptibility to weeds, disease and pests.
• Marine Food Chain can be killed with
significant UV Radiation.
• Lesser amounts of UV Radiation causes
slowdown of Photosynthesis.
OBLIGATIONS OF MARINE
FRATERNITY
• Do not vent out CFCs and HCFCs into
the atmosphere.
• Use CFC to HFC conversion kits that are
available for existing equipment.
• When ordering for new Equipment
/Machinery for Refrigeration and Air
Conditioning, ensure to use only HFC
Refrigerant based Machinery.
• Educate and Train the floating staff
regarding the importance of these steps.
Reefer Cargo Temperature Log
M/V ___________________________
VOY NO. __________
SAILED PORT ___________________
ON : ____________
Note : All temperatures to be entered in Degrees Celsius
DATE
TIME
Pulp temp
A DECK
Co2
Humidity
Pulp temp
B DECK
Co2
Humidity
Pulp temp
HOLD NO
C DECK
Co2
Humidity
Pulp temp
D DECK
Co2
Humidity
Pulp temp
E DECK
Co2
Humidity
ARRIVED PORT ___________________
ON : ____________