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Tanker safety guide chemical four edition 2014


TANKER SAFETY GUIDE
CHEMICALS
FOURTH EDITION

INTERNATIONAL CHAMBER OF SHIPPING


INTERNATIONAL CHAMBER OF SHIPPING
Established in 1921, the International Chamber of Shipping (ICS) is the principal international trade association
for shipowners, representing the global industry at IMO and the other international bodies that impact o n
shipping. Its membership comprises national shipowners' associations from 36 countries, covering all sectors and
trades and over 80% of the world merchant fleet.

Wh ile the advice given in this Guide has been developed using the best information available, it is to be followed
at the users' own risk. No responsibility is accepted by Maritime International Secretariat Services Limited, or by
the International Chamber of Shipping Limited, or by any firm, corporation or organisation who or which has
been in any way concerned with the furnishing of data, the compilation, publication or authorised translation,
supply or sale of this guidance, for the accuracy of any information or advice given herein, or any omission
herefrom or consequences whatsoever resulting directly or indirectly from use of this Guide, or from compliance
with or adoption of guidance contained herein, even if caused by a failure to exercise reasonable Cilre.


INTERNATIONAL CHAMBER OF SHIPPING

TANKER SAFETY GUIDE (CHEMICALS)
FOURTH EDITION
Published by Maritime International Secretariat Services Limited
38 St Mary Axe, London, EC3A 8BH
Tel
Email
Web

+44 20 7090 1460
publications@marisec.org
www.ics-shipping.org

© Maritime International Secretariat Services Limited 2014
No translation of this guide into a foreign language may be made without the express permission of Maritime
International Secretariat Services Limited.

2

TANKER SAFETY GUIDE (CHEMICALS)


FOREWORD TO THE FOURTH EDITION
The first edition of the ICS Tanker Safety Guide (Chemicals) was published in 1971 and complemented the
first International Maritime Organization (IMO) Code for the Construction and Equipment of Ships Carrying
Dangerous Chemicals in Bulk. The ICS Guide was developed from a clear demand, from shipping companies and
seafarers, for advice on best practice with respect to safety at sea.
The ICS Guide has si nce become the standard reference work on chemical tanker operations, with subsequent
editions taking particular account of the need for chemical tankers to comply with additional IMO regulations
to ensure the prevention of pollution. It is recommended that a copy should be carried on board every tanker
engaged in the carriage of chemicals by sea.
This fourth edition of the Guide is the result of substantial revision and updating. In response to feedback from
users, and i n order to improve access to important information, much of the content from the previous edition's
appendices has been incorporated i nto the mai n body of the text, while being completely redrafted in the
interests of improved understanding.
The latest Guide reflects the continui ng need for guidance on well established i ndustry best practice, but
also takes account of more recent developments which have emerged in the chemical trades. In particular, it
should be noted that this updated edition addresses IMO's adoption, in May 2014, of important new SOLAS


requirements for the fitting and use of inert gas on board ch emical tankers. This followed an in depth IMO
review of tanker safety- in which ICS participated - that has taken th e best part of a decade.
Earlier editions of this ICS Guide provided advice on the precautions to be taken prior to entering enclosed
spaces and cargo tanks. In the i nterveni ng years, serious enclosed space accidents have unfortunately
continued to occur, primarily due to a failure to follow establish ed procedures. The need for updated and
improved guidance on this most important safety topic has therefore been given even greater emphasis, with
separate chapters dedicated to both enclosed space entry precautions and to the correct use of nitrogen as an
inerting medium.
A new feature introduced in this edition is the use of yellow coloured text boxes. These contain a summary of
information of adjacent text regarding a particular safety issue. Although readers should pay particular attention
to the advice provided in th ese yellow boxes, it should be understood that these only serve to amplify the main
text, and that a full and careful reading of all advice relating to a particular subject is essential in order to achieve
a comprehensive understanding.
Following the example of the previous edition, a model Material Safety Data Sheet (MSDS) has been i ncluded to
encourage the presentation of data in a standard format. This is particularly important w ith regard to emergency
and first aid information, which needs to be readily identifiable and in a common layout. When a ship is at sea,
or at a remote terminal, external assistance may not be available, and easily accessible emergency advice is
therefore vital.
Emphasis also continues to be given to the importance of ships and terminals completing the Ship/Shore Safety
Checklist in advance of conducting any cargo operations in port, with a revised Checklist and full guidance for
completion being incorporated as Appendices.
Last but not least, particular attention has been given to th e best means of instilling an effective safety culture
throughout ch emical tanker operations, in which everyone involved thinks of 'safety first' and f ully understands
that virtually every unsafe action is preventable.
No Guide of this nature can ever be complete, however much care and effort has gone into its preparation.
Comments and suggestions for improvements to the Guide are therefore always welcome, and should be
addressed to:
International Chamber of Shippi ng
38 St Mary Axe
London EC3A 8BH
E-mail: info@ics-shippi ng.org

3


PURPOSE AND SCOPE
The purpose of this ICS Guide is to provide those serving on ships carrying hazardous and noxious chemicals i n
bulk with up to date information on recognised good practice i n safe and pollution free operations.
This Guide is i ntended for use on ships regulated under MARPOL Annex II (Regulations for the Prevention of
Pollution by Noxious Liquid Substances) i ncluding oil tankers operating in accordance with Annex II when they
are carrying chemical cargoes. However, its contents are also relevant inter alia to shipping company managers,
cargo i nterests, training i nstitutes and terminal operators.
The Guide is intended to be compatible with the International Safety Guide for Oil Tankers and Terminals
(ISGOTI) in order to provide consistent safe advice and also to minimise the increasing burden associated with
audits and vetti ng inspections. This Guide is also a companion to the ICS Tanker Safety Guide (Liquefied Gas).
The Guide's recommendations cannot cover every possible situation that may be encountered on a chemical
tanker, but they do provide wide general guidance on safe procedures and safe worki ng practices when handling
and transporting chemicals in bulk.
In the interests of consistent and uniform safe working practices, it is recommended that a copy of this Guide
be kept - and used - on board all chemical tankers. Chemical tankers should also have on board ISGOTI, which
should be consulted in conjunction with this Guide, especially whenever oil cargoes are carried.
The Guide deals primarily with operational matters and good safety practices. It does not make
recommendations on the construction or maintenance of chemical carriers or their equipment: such standards
are set by IMO, national administrations and classification societies. Likewise, the Guide does not address the
operation of specific items of equipment or their repair. In some cases, however, general reference is made to
these matters as well as to relevant regulations.
It should be noted that this Guide is not i ntended to address commercial matters such as tank cleani ng
standards, cargo quality maintenance or equipment performance, which (consistent w ith IMO regulations) may
be determined by industrial practices and the requirements of cargo owners.

CONTENTS OF CD ACCOMPANYING THIS GUIDE
The CO accompanying this fourth edition contains the full text of the Guide with a 'search function'.
The CO also contains printable/amendable versions of most appendices.

IMPORTANT NOTE

It is emphasised that this Guide is intended to complement, not supersede, any company safety and
operational guidelines or ship emergency plans, including safety management procedures required by
the IMO International Safety Management (ISM) Code. It should also be borne in mind that in all cases
the advice given may be subject to local or national regulations, and that terminal operators have their
own safety procedures which could affect cargo handling operations and the measures to be adopted
in emergencies. The Master and all personnel must be aware of and comply with those regulations and
procedures. Their existence will be highlighted by the use of the Ship/Shore Safety Checklist included in
Appendix 3 of this Guide which, together with its guidelines for completion, remains a fundamental part
of establishing safe conditions for transport by sea of chemicals in bulk.

4

TANKER SAFETY GUIDE (CHEMiCAL5)


ACKNOWLEDGMENTS
This edition of the ICS Tanker Safety Guide (Chemicals) continues the tradition of providing a consolidation of
experience and best operating practice in the chemical tanker industry. Its production would not have been
possible without the assistance of those i ndividuals, companies and organisations that have so generously given
thei r time and expertise to ensure its accuracy in the interests of the safe carriage of chem icals by sea.
Special gratitude is expressed to the dedicated members of the technical working group, who spent many
meetings making sure that the text was both accurate and that it reflects industry best practice - Toralf S0renes
of Odfjell (Chairman of the group), Arjan Kreuze of Jo Tankers, Bruno Caillard representi ng Armateurs de France,
Jan Sloth M0ller of Maersk, Keith Dean of Stolt Tankers, Leif Gunnar Alvaer of Odfjell, Per Tyrsted Jorgensen of
Eitzen Chemical, Per Winther Christensen of the Danish Shipowners' Association and Peter Maasland of Shell.
Particular mention is also made of the following i ndustry associations: the Chemical Distribution Institute
(COi), the International Parcel Tankers' Association (IPTA), the International Association of lndependant Tanker
Owners (lntertanko) and th e Oil Companies International Marine Forum (OCIMF). These organisations have
ki ndly provided a 'peer review' of the fourth edition in order to verify that the contents meet the needs of
the wider industry and their advice and comments have been carefully considered in the d rafti ng of this
industry publication.

5


CONTENTS
PAGE

6

FOREWORD TO THE FOURTH EDITION

3

PURPOSE AND SCOPE

4

DEFINITIONS

15

CHAPTER 1 - HAZARDS AND PROPERTIES OF CHEMICALS

21

1.1

Introduction

23

1.2
1.2.1
1.2.2
1.2.3
1.2.4
1.2.5
1.2.6
1.2.7
1.2.8

Physical Properties
Density and specific gravity
Volume expansion coefficient
Melting point
Vapour pressure

23

Boiling point
Vapour density
Viscosity
Water solubility

1.3
1.3.1
1.3.2

Flammability
Flash point
Explosive/flammable limits

26
26
26

1.4
1.4.1
1.4.2
1.4.3
1.4.4
1.4.5
1.4.6

Static Electricity
General
Charge accumulation and relaxation in liquids
Generation of static
Static generation during cargo operations
Static generation during tank cleaning
Static generating portable equipment

28
28
28
28
29
29
29

1.5
1.5.1
1.5.2
1.5.3
1.5.4
1.5.5

Toxicity
General

30
30
30
30
31
31

Exposure to toxicity
Degrees of toxicity
Exposure limits
Precautionary principles

1.6
1.6.1
1.6.2
1.6.3
1.6.4
1.6.5
1.6.6
1.6.7

Chemicals that react with oxygen
Chemicals that react with water
Reaction of acids w ith water
Incompatible chemicals
Reaction with construction materials

1.7
1.7.1
1.7.2

Corrosive Substances
General
IBC Code requirements

Reactivity
General
Unstable chemicals

TANKER SAFETY GUIDE (CHEMiCAL5)

23
23

24
25
25
25
25
26

31
31

32
34
34
35
35

37
37
37
38


1.8
1.8.1
1.8.2
1.8.3

Hazardous Cargo Information
Material Safety Data Sheet
Contents of a Material Safety Data Sheet
Inhibited cargoes

CHAPTER 2 - GENERAL PRECAUTIONS
2.1

38
38
38
39

41

Introduction

43

2.2

Moorings

43

2.3

Emergency Towing -off Pennants (Fi rewires)

43

2.4
2.4.1
2.4.2
2.4.3
2.4.4

Access to the Ship
Means of access (gangways or accommodation ladders)
Lighting
Unau1horised persons
Persons smoking or intoxicated

43
43

2.5
2.5.1
2.5.2

Warning Notices
Permanent
Temporary

44
44
44

2.6
2.6.1
2.6.2

Effects of Other Ships and Berths
Other tankers at adjacent berths
Chemical carrier operations at general cargo berths

45
4S
4S

2.7
2.7.1
2.7.2
2.7.3
2.7.4

Weather Precautions
Wind conditions
Electrical storms
Cold weather
Openings to the accommodation

45
4S
4S
4S
46

2.8
2.8.1
2.8.2
2.8.3

Machinery Spaces
Funnel sources of ignition
Blowing boiler tubes
Cargo vapour

46
46
46
46

2.9
2.9.1
2.9.2

Pressure Surges
Introduction
Generation of pressure surge

47
47
47

2.10
2.10.1
2.10.2

Pumprooms and Enclosed Spaces
Cargo pumprooms
Enclosed spaces

48

2.11

Ship's Readiness to Move

48

2.12

Helicopter Operations

48

2.13
2.13.1
2.13.2
2.13.3
2.13.4

Communication Equipment
Ship's radio transmission equipment
Electrical maintenance and repairs
Transmitting devices
Personal electronic items

49
49
49
49

2.14
2.14.1
2.14.2
2.14.3
2.14.4
2.14.S
2.14.6
2.14.7

Hot Work
General
Assessment of hot work
Hot work permit
Preparation for hot work
Checks by officer responsible for safety during hot work
Action on completion of hot work
Hot work flow chart

44
44
44

48
48

so
50

so
so
Sl
Sl
S2
S2
S3

7


2.15

Cold Work

54

2.16

Mechanically Powered Tools

54

2.17

Hand Tools

54

CHAPTER 3 - SAFETY MANAGEMENT, TRAINING AND PPE

8

SS

3.1

Introduction

57

3.2
3.2.1
3.2.2

Impl ementing a Safety Culture
What is a safety culture?
Key features of an effective safety culture

57
57
58

3.3

The ISM Code

58

3.4

Company Responsibility

58

3.5

Safety Information for Shore Personnel

59

3.6

Outside Contractors

59

3.7
3.7.1
3.7.2
3.7.3

Risk Management
Risk assessment terms
Conducting risk assessments
Risk assessment matrix

59
60
60
61

3.8
3.8.1
3.8.2

Safe Operations
Routine operations
Non-routine operations

61
61
62

3.9

Incident Investigations

63

3.10
3.1 0.1
3.1 0.2
3.1 0.3
3.1 0.4
3.1 0.5
3.1 0.6
3.1 0.7
3.1 0.8
3.1 0.9
3.1 0.10

Ship's Manning
Responsibility
Familiarisation
Tanker specific training requirements
Basic tanker training
Advanced tanker training
Crew communication
Drills and exercises
Crew schedules and minimum hours of rest
Summary of STCW requirements - hours of work and rest
Prevention of drug and alcohol abuse

63
63
64
64
64
65
65
66
66
66
67

3.11
3.11 .1
3.1 1.2
3.1 1.3
3.11 .4
3.1 1.5
3.11 .6
3.11 .7
3.1 1.8
3.11 .9
3.11 .10
3.1 1.11
3.11 .12
3.11 .13
3.1 1.14
3.11 .15
3.11 .16
3.1 1.17

Personal Protective Equipment (PPE)
Atmosphere monitoring equipment
Safe working clothing
Protective clothing
Toxic or corrosive substance protection
Chemical resistant clothing (protective suits)
Types of chemical resistant clothing
Eye protection
Hand protection
Foot protection
PPE matrix
Respiratory protection
Canister or filter type respirators
Self-Contained Breathing Apparatus (SCBA)
Air line breathing system
Emergency escape respiratory protection
Maintenance
Training

67
67
68
68
68
69
69
73
73
73
73
74
74
74
75
75
75
75

TANKER SAFETY GUIDE (CHEMiCAL5)


CHAPTER 4 - REGULATORY FRAMEWORK

77

4.1

Introduction

79

4.2

Regulatory Guidelines

79

4.3
4.3 .1

IMO MARPOL Regulations
MARPOL Annex I - Prevention of Pollution by Oil
MARPOL Annex II - Prevention of Pollution by Noxious Liquid Substances
MARPOL Annex VI - Prevention of Air Pollution from Ships

79
80

83

4.4.1
4.4.2
4.4.3
4.4.4

IMO International Code for the Construction and Equipment of
Sh ips carrying Dangerous Chemicals in Bulk (IBC Code)
Tank types
Summary of IBC Code requirements
lnerting and padding
Damage stability

4.5

Inert Gas Requirements for Chemical Carriers

87

4.6

IMO Ballast Water Convention

88

4.3 .2
4.3.3

4.4

CHAPTER 5 - SHIP AND EQUIPMENT

81

83

84
86
86

87

89

5.1

Introduction

91

5.2

cargo Tanks

91

5.3

Monitoring Equipment
Introduction
Alarms and shutdowns
Air supply to control systems
Liquid level gauges
Overfill detection systems
Pressure indicating devices
Temperature monitoring equipment

92

Atmosphere Monitoring
General
General precautions
Oxygen analysers
Flammable gas detectors
Toxic gas detectors

98
98
98

5.3 .1
5.3 .2
5.3.3
5.3.4
5.3.5
5.3 .6
5.3.7

5.4
5.4.1
5.4.2
5.4.3
5.4.4
5.4.5

5.5

92
93
94
94
96
96
97

99
100
101

103

5.5.1

cargo Pumps
General

5.5.2
5.5.3
5.5.4
5.5.5

Oeepwell pumps
Cargo pumprooms
Booster pumps
Emergency cargo pumps

5.6

Piping Systems and Valves

105

5.7

cargo Manifold

106

5.8

Venting Systems and P/V Valves

107

5.9

Vapour Return Systems

108

5.10

Heating and Cooling Systems

109

5.11

Tank Washing Systems
Fixed tank washing machines
Portable tank washing machines and hoses

110
110

5.11 .1
5.11 .2

103
103
104
104
105

111

9


5.12
5.12.1
5.12.2
5.12.3

Venting outlets

111
111
111
111

5.13
5.13.1
5.13.2
5.13.3
5.13.4
5.13.5
5.13.6
5.13.7
5.13.8

Inert Gas Systems
Introduction
Oxygen content
Sources of inert gas
Compressed nitrogen stored on board
Liquid nitrogen stored on board
Pressure swing adsorption (PSA) nitrogen generators
Mem brane separation nitrogen generators
Oil fired inert gas generators

112
112
112
113
113
114
114
114
115

5.14
5.14.1
5.14.2
5.14.3
5.14.4
5.14.5

Cargo Hoses
Introduction
Certification, marking and testing
Storage and maintenance
Operational use
Cargo hose connections

115
115
115
115
116
116

5.15
5.15.1
5.15.2
5.15.3

Electrical Equipment and Installations in Hazardous Areas
Introduction
Certified safe electrical equipment
Bonding and earthing

118
118
118
118

5.16

Ballast Pumprooms

119

5.17

Openings in Deckhouses and Superstructures

119

Gas Freeing Equipment
Permanently installed gas freeing equipment
Portable gas freeing equipment

CHAPTER 6 - CARGO OPERATIONS

10

121

6.1

Introduction

123

6.2
6.2.1

Responsibility
Personnel and resources

123
123

6.3
6.3.1
6.3.2
6.3.3
6.3.4
6.3.5

Planning Cargo Operations
Introduction
Cargo information
IMO Certificate of Fitness
Stowage planning
Specific cargo handling requirements

124
124
124
124
125
125

6.4
6.4.1
6.4.2
6.4.3
6.4.4
6.4.5

Preparation for Cargo Operations
Introduction
Pre-arrival information exchange
Cargo handling plan
Ship's personnel
Preparing the cargo system prior to arrival

128
128
128
129
130
131

6.5
6.5.1
6.5.2
6.5.3
6.5.4

Port Arrival Procedures
Pre-transfer meeting
Ship/shore communications during cargo operations
Ship/Shore Safety C hecklist
Action prior to commencing transfer operations

133
133
134
134
134

6.6

Monitoring cargo Operations

135

6.7
6.7.1

Cargo Transfer Operations
Inspection of cargo tanks prior to loading

136
136

TANKER SAFETY GUIDE (CHEMICALS)


Sampling and gauging
Sample management
Sampling systems
Sample storage
Ballasting and deballasting in port
Clearing shore pipelines
Completion of transfer
Disconnection of cargo hoses
Cargo unloading
lnerting and tank atmosphere control during unloading
Sweeping of cargo residues
Completion of discharge

137
138
139
140
140
141
141
142
143
144
14S
14S
146
147
147
148
149
149
149
149
1SO

6.8
6.8.1
6.8.2
6.8.3
6.8.4
6.8.5
6.8.6

cargo care During the Voyage
Tank integrity
Tank venting
Temperature controlled cargoes
Inhibited cargoes
Maintaining an inert atmosphere during the voyage
Ballasting cargo tanks

151
1Sl
1Sl
1Sl
1Sl
1S2
1S2

6.9
6.9.1
6.9.2
6.9.3
6.9.4
6.9.5
6.9.6
6.9.7
6.9.8

Sh ip to Ship Transfer
General

152
1S2
1S3
1S3
1S4
1S4
1S4
1S4
1SS

6.7.2
6.7.3
6.7.4
6.7.5
6.7.6
6.7.7
6.7.8
6.7.9
6.7.10
6.7.11
6.7.12
6.7.13
6.7.14
6.7.1s
6.7.16
6.7.17
6.7.18
6.7.19
6.7.20
6.7.21
6.7.22

Manifold connections
Cargo loading
Ship/shore electric currents
Cargo pumprooms
Correct operation of PN valves
Vapour return and vapour balancing
Tank atmosphere control
Dangers of pressurised loading
Topping off procedure

Responsibility
Communications
Navigational warnings
Weather conditions and limitations
Pre-transfer preparations on each ship
Cargo transfer operations
Completion of cargo transfer

CHAPTER 7 - INERT GAS AND NITROGEN SAFETY

157

7.1

Introduction

159

7.2

Dangers of Nitrogen

159

7.3

Safe Operations Involving Nitrogen

160

7.4
7.4.1
7.4.2
7.4.3
7.4.4
7.4.5
7.4.6
7.4.7
7.4.8
7.4.9

lnerting Operations
lnerting definitions
Maintenance of an inert atmosphere

161
161
161
162
162
163
163
163
163
163

lnerting tanks containing cargo
lnerting empty tanks
Loading inerted tanks
Maintaining inerted tanks during the voyage
Maintaining an inert atmosphere during unloading
Tank cleaning and gas freeing under inert conditions
Nitrogen supplied from shore

11


CHAPTER 8 - TANK CLEANING AND GAS FREEING
8.1

Introduction

169

8.2

Procedures and Arrangements Manual

169

8.3
8.3.1
8.3.2
8.3.3
8.3.4

Supervision and Preparation
Responsibility
Tank cleaning plan
Pre-cleaning meeting
Preparations

169
169
169
170
170

8.4
8.4.1
8.4.2
8.4.3
8.4.4
8.4.5
8.4.6
8.4.7
8.4.8

Cargo Tank Washing and Cleaning
General
Tank washing atmospheres
Prevention of toxic exposure during tank cleaning
Prevention of static generation during tank cleaning
Tank washing in an inert atmosphere
Tank washing in a non-inert atmosphere
Precautions for sounding tanks
Transfer of wash water to slop tanks

171
171
171

8.5
8.5.1
8.5.2
8.5.3
8.5.4
8.5.5
8.5.6
8.5.7

Special Cleaning Methods
Introduction
Reactive cargoes
Manual cleaning
Use of tank cleaning additives
Steaming
Recirculation washing
Cleaning or gas freeing of cargo from non-cargo spaces

174
174
175
175
176
176
176
176

8.6
8.6.1

Monitoring Tank Cleaning Operations
Precautions for sounding tanks when not using a sounding pipe

177
177

8.7
8.7.1
8.7.2
8.7.3

Arrangements for the Disposal of Tank Washings and Sl ops
General
Management of slops
Mandatory prewash water

177
177
177
177

8.8

Tank Clean ing in Port

178

8.9

Tank Clean ing Equipment

178

8.10
8.10.1
8.10.2

Gas Freeing
Safe procedures for gas freeing after tank cleaning and cleaning by ventilation
Opening up of cargo lines and handling equipment

178
178
179

CHAPTER 9 - ENTRY INTO ENCLOSED SPACES

12

167

172
172
173
173
174
174

181

9.1

Introduction

183

9.2
9.2.1
9.2.2
9.2.3
9.2.4

Hazards
Oxygen deficiency
Toxic and/or flammable gases
Presence of inert gas including nitrogen
Oxygen enrichment

183
185
185
185
185

9.3

Atmosphere in Enclosed Spaces

186

9.4
9.4.1
9.4.2

Requirements for Enclosed Space Entry
Planning
Entry permit

186
187
187

TANKER SAFETY GUIDE (CHEMICALS)


9.5

Testing Before Entry

189

9.6
9.6.1

Enclosed Space Entry
Entry into enclosed spaces other than cargo tanks

190
191

9.7

Work in Enclosed Spaces

191

9.8

Entry into an Enclosed Space where the Atmosphere is Known
or Suspected to be Unsafe

192

9.9
9.9.1
9.9.2
9.9.3
9.9.4
9.9.5

Rescue from Cargo Tanks and Other Enclosed Spaces
General

193
193
193
193
194
195

Preventing enclosed space accidents
Rescue and recovery organisation
The rescue operation
Rescue and recovery equipment

CHAPTER 10 - EMERGENCY PROCEDURES

197

10.1

Introduction

199

10.2
10.2.1
10.2.2
10.2.3
10.2.4

Emergency Organisation
Emergency team
Supporting crew
Emergency organisation in port
Vacating a berth or terminal in an emergency

199
199
199
200
200

10.3
10.3.1
10.3.2
10.3.3
10.3.4
10.3.5
10.3.6
10.3.7
10.3.8
10.3.9

Fire-Fighting Equipment
General
Water
Foam
Foam monitors
Carbon dioxide
Halon
Dry powder
Inert gas systems
Fire-fighting clothing

200
200
200
201
201
201
201
202
202
202

10.4
10.4.1
10.4.2
10.4.3
10.4.4

Responding to Emergencies
Emergencies involving fire
Emergency response to fire
Fires involving chemicals
Action to take in the event of fire

202
202
203
203
204

10.5
10.5.1
10.5.2
10.5.3
10.5.4

Other Emergencies
Chemical cargo spills
Deck valve and deck pipeline leakage
Tank leakage within the vessel
Emergency discharge or jettison of cargo

204
204
205
206
206

10.6

Notification of Spillage

207

10.7
10.7.1
10.7.2
10.7.3
10.7.4
10.7.5

Exposure to Chemicals
Planning
Medical first aid guides
Toxic cargoes and antidotes
Medical first aid after exposure to chemicals
Emergency information on MSDS

207
207
207
207
208
208

10.8

First Aid and Further Care

209

13


APPENDICES

211

Appendix 1

Visitor Information Card

213

Appendix 2

Hot Work Permit

216

Appendix 3

Ship/Shore Safety Checklist

220

Appendix 4

Ship/Shore Safety Checklist Guidelines

227

Appendix S

Material Safety Data Sheet (MSDS)

245

Appendix 6

Inhibited Cargo Certificate

2S1

Appendix 7

Enclosed Space Entry Permit

2S2

Appendix 8

Cargo Hose Record

2S6

Appendix 9

Flexible Hose Test Certificate

2S7

Appendix 10

PPE Matrix

2S8

Appendix 11

Relevant Industry Publications

2S9

INDEX

14

TANKER SAFETY GUIDE (CHEMICALS)

261


DEFINITIONS
For the purpose of this Guide the following interpretations apply.
Administration (flag state)

The maritime administration of the country in which the ship is registered.
This is the authority that is responsible for the issuance of statutory certificates
related to the operation of a ship, and is responsible for inspections to ensure
compliance with appropriate standards.

Administration (port state)

The administration of the country in which a port is situated.

Approved equipment

Equipment of a design that has been tested, approved and certified by an
appropriate authority, such as a flag state administration or classification
society, as safe for use, for example, in a specified hazardous atmosphere.

Asphyxia

The condition arising when the blood is deprived of an adequate supply of
oxygen so that loss of consciousness may follow.

Asphyxiant

A gas or vapour, which may or may not have toxic properties, which when
present in sufficient concentrations excludes oxygen and leads to asphyxia.

Auto-ignition temperature

The lowest temperature to which a solid, liquid or gas needs to be raised to
cause self-sustaining combustion without initiation by a spark or flame or
other source of ignition.

Boiling-Liquid/Expanding Vapour Explosion (BLEVE)

An explosion typically resulting from a catastrophic failu re of a vessel
containing a liquid significantly above its boiling point at normal
atmospheric pressure.

Boiling point

The temperature at which the vapour pressure of a liquid equals that of the
atmosphere above its surface; this temperature varies with pressure.

Bonding (electrical)

The connecting together of electricity conducting metallic objects to ensure
electrical continuity.

Cargo area

That part of the ship which contains the whole cargo system, cargo pump rooms,
and includes the full beam deck area over the length of the ship above the cargo
containment system. Where fitted, the cofferdams, ballast or void spaces at the
after end of the aftermost cargo space - or the forward end of the forward most
cargo space - are regarded as being excluded from the cargo area.

Cargo operations

Any operations involving the handling of cargo, tank cleaning, purging or
venting etc.

Cargo transfer

The transfer of cargo to or from the ship.

Cavitation

Uneven flow caused by vapour pockets within a liquid .

15


Certificate of Fitness

A certificate issued by the flag administration confirming that the structure,
equipment, fittings, arrangements and materials used in the construction
of a chemical carrier are in compliance with the IMO IBC Code. Such
certification may be issued on behalf of the administration by approved
classification societies.

Certified gas free
(see also Gas free)

A term signifying that a tank, compartment or container has been tested by
an authorised person using an approved testing instrument, and found to be
in a suitable condition - i.e. not deficient in oxygen and sufficiently free from
toxic and chemical gases - for a specified activity, such as tank entry.

Certified safe el ectrical
equipment
Chemical absorption
detector

(See Approved equipment)

An instrument used for the detection of gases or vapours which works on the
principle of a reaction between the gas and a chemical agent in the apparatus;
the gas discolours the agent or the agent dissolves some of the gas.

Closed gauging system
(closed ullaging)

A system in which the contents of a tank can be measured by means of
a device which penetrates the tank, but which is part of a c.losed system
preventing the release of tank contents.

Cofferdam

The isolating space between two adjacent steel bulkheads or decks; it may be
a void or ballast space.

Combustible gas detector

An instrument for detecting a flammable gas/air mixture and usually
measuring the concentration of gas in terms of its Lower Flammable Limit
(LFL). No single instrument is reliable for all combustible vapour.

Enclosed space

A space which has any of the following characteristics:
l imited openings for entry and exit;
Inadequate ventilation; or
Is not designed for continuous worker occupancy, and includes, but is not
limited to, cargo spaces, double bottoms, fuel tanks, ballast tanks, cargo
pump rooms, cargo compressor rooms, cofferdams, cha in lockers, void
spaces, duct keels, inter-barrier spaces, boilers, engine crankcases, engine
scavenge air receivers, sewage tanks, and adjacent connected spaces.
This list is not exhaustive and a list should be produced on a ship by ship basis
to identify enclosed spaces.

Explosion proof/flame
proof equipment

Equipment or apparatus which will withstand, without damage and in
accordance with its prescribed rating (including recognised overloads), any
explosion of a prescribed flammable gas to which it may be subjected under
practical operating conditions and which will prevent the transmission of
flame to the surrounding atmosphere.

'Expl osimeter'

11>

TANKER SAFETY GUIDE (CHEMICALS)

(See Combustible gas detector)


Filling limit (or ratio)

That volume of a tank, expressed as a percentage of the total volume, which
can be safely filled, having regard to the possible expansion (and change in
density) of the liquid.

Flame arrester

A device used in gas vent lines to arrest the passage of flame into
enclosed spaces.

Flame proof equipment

(See Explosion proof equipment)

Flame screen (gauze screen)

A portable or fitted device incorporating one or more corrosion resistant
wire woven fabrics of very small mesh used for preventing sparks from

entering a tank or vent opening, or for a short period of time preventing the
passage of flame, yet permitting the passage of gas (not to be confused with
Flame arrester).
Flammable

Capable of being ignited and burning in air.

Flammable gas

A vapour/air mixture within the flammable range.

Flammable limits

The minimum and maximum concentrations of vapour in air which form
explosive (flammable) mixtures are known as the Lower Explosive Limit (LEL)
and Upper Explosive Limit (UEL) respectively. (For the purpose of this Guide,
these terms are synonymous with Lower Flammable Limit (LFL) and Upper
Flammable Limit (UFL) respectively.)

Flammable range

The range of flammable vapour concentrations in air between the lower
and upper flammable limits. Mixtures within this range are capable of being
ignited and burning.

Flash point

The lowest temperature at which a liquid gives off sufficient vapour to form
a flammable mixture with air near the surface of the liquid or within the
apparatus used . This temperature is determined by laboratory testing in a
prescribed apparatus.

Gas absorption detector

(See Chemical absorption detector)

Gas dangerous space
or zone

A space or zone within the cargo area which is designated as likely to contain
flammable vapours and which is not equipped with approved arrangements to
ensure that its atmosphere is maintained in a safe condition at all times.

Gas detector

An instrument which alerts someone to the presence of gas, especially in
spaces where gas is not normally expected.

Gas free

Gas free means that a tank, compartment or container has been tested using
approved gas detection equipment and found to be sufficiently free, at the
time of the test, from toxic, flammable or inert gases for a specified activity,
such as tank entry.

Gas freeing

Gas freeing means the process where a portable or fixed ventilation system is
used to introduce fresh air into a tank in order to reduce the concentration of
hazardous gases or vapours to a level safe for tank entry.

17


18

Gauze screen

(See Flame screen)

Hot work

Work involving flames, incendive sparks or temperatures likely to be
sufficiently high to cause ignition of flammable gas. The term includes any
work involving the use of welding, burning or soldering equipment, blow
torches, some power driven tools, portable electrical equipment which is not
intrinsically safe or contained in an explosion proof housing, and equipment
with internal combustion engines.

Hot work perm it

A document issued by a person authorised by the Master permitting specific
work to be done, for a specified time in a defined area, employing tools and
equipment which could cause ignition of flammable gas (see Hot work).

IMO

The International Maritime Organization is the United Nations specialised
agency responsible for developing international regulations for safety at sea
and pollution prevention.

lncendive spark

A spark of sufficient temperature and energy to ignite flammable gas.

Inert gas

A gas (e.g. nitrogen) or mixture of gases containing insufficient oxygen to
support combustion.

lnerting

The introduction of inert gas into a space to reduce and maintain the oxygen
content at a level at which combustion cannot be supported.

Inflammable

(See Flammable)

Inhibited cargo

A cargo which contains an inhibitor.

Inhibitor

A substance used to prevent or retard cargo deterioration or a potentially
hazardous chemical self-reaction, e.g. polymerisation.

Insulating flange

An insulating device placed between metallic flanges, bolts and washers, to
prevent electrical continuity between pipelines, sections of pipelines, hose
strings and loading arms, or equipment/apparatus.

Intrinsically safe

Intrinsically safe equipment, instruments, or wiring that are incapable of
releasing sufficient electrical or thermal energy, under normal or abnormal
conditions, to cause ignition of a specific hazardous atmospheric mixture in its
most easily ignited concentration.

lower Explosive limit

LEL (see Flammable limits)

lower Flammable limit

lfl (see Flammable limits)

MAK

MAK values are daily eight hour time weighted average allowable values for
exposure to chemicals in the workplace applicable to healthy adults.

MARPOL

International Convention for the Prevention of Pollution from Ships.

TANKER SAFETY GUIDE (CHEMICALS)


Material Safety Data
Sheet (MSDS)

Document containing information and instructions on hazardous materials.
A MSDS contains details about hazards and risks relevant to the substance,
requirements for its safe handling, and actions to be taken in the event of fire
or exposure to the product. MSDS is synonymous with SOS.

Oil Discharge Monitoring
Equipment (ODME)

COME is equipment required on oil tankers as part of the approved oil
discharge and monitoring control system. It is used to m onitor the discharge
into the sea of oily ballast or other oil contaminated water from the cargo
tank areas.

OH

Occupational Exposure l imits (OELs) are intended to help to control exposure
to dangerous substances in the workplace, by setting the maximum amount
of (air) concentration of a substance that can safely be allowed. The average
exposure time in OEL lists is normally eight hours per day (often referred to as
TWA-Sh or Time Weighted Average - Sh).

Oxygen analyser

An instrument used to measure oxygen concentrations, expressed as a
percentage by volume.

Oxygen level
in atmosphere

Throughout this Guide the percentage of oxygen in air is referred to as 21 %,
since most instrumentation in use on ships has a gauge or scale which reads to
21 % . Strictly, however, the percentage of oxygen falls several hundredths of a
percent below that figure, variously quoted between 20.85% and 20.95%.

Padding

Filling and maintaining the cargo tank and associated p'iping system with
an inert gas - or other gas, vapour or liquid - in order to separate the cargo
from air.

Polymerisation

The phenomenon by which the molecules of a particular compound link
together into a larger unit containing anything from two to thousands of
molecules, the new unit being called a polymer.

Purging

Purging means the introduction of inert gas into a tank which is already in
an inert condition with the object of further reducing the oxygen content
and/or reducing the content of existing hydrocarbon or other flammable
vapours to a level below which combustion cannot be supported if air is
subsequently introduced into the tank.

Relative vapour density

The mass of the vapour compared w ith the mass of an equal volume of air,
both at standard conditions of temperature and pressure. Thus vapour density
of 2.9 means that the vapour is 2.9 times heavier than an equal volume of air
under the same physical conditions.

Responsible officer

The Master or any officer to whom the Master may delegate responsibility for
any operation or duty.

Responsible terminal
representative

The shore supervisor in charge of all operators and operations at the terminal
associated with the handling of products, or responsible delegate.

Restricted gauging system
(also known as restricted
ullage system)

A system employing a device which penetrates the tank and which, when in
use, permits a small quantity of cargo vapour or liquid t o be released. When
not in use the device is completely closed.

19


Sloshing

Wave formations which may arise at the liquid surface in a cargo tank from
the effects of ship motions.

SOLAS

International Convention for the Safety of Life at Sea.

Span gas

A vapour sample of known composition and concentration used to calibrate
(or span) a ship's gas detection equipment.

Specific gravity

The ratio of the weight of a volume of a substance at a given temperature
to the weight of an equal volume of fresh water at the same temperature
or at a different given temperature. (Since temperat ure affects volume, the

temperature at which a specific gravity comparison is made needs to be
known and is stated after the ratio.)
Static electricity

The electrical charge produced on dissimilar materials through physical contact
and separation.

Threshold limit Value

The 'time weighted average' (fWA) concentration of a substance to which it is
believed workers may be repeatedly exposed, for a normal eight hour working
day and 40 hour working week, day after day, without adverse effect. It may
be supplemented by a 'short-term exposure limit' (STEL).

(TLV)

Toolbox talk

A short informal safety talk at the workplace prior to conducting planned
work. Its objective is to raise awareness of all relevant aspects of the planned
work, and particularly to discuss procedures and safety requirements.

Tripartite agreement

Where it is proposed to carry a liquid substance in bulk which has not been
included in the IBC Code, the appropriate authorities invol ved in the proposed
operation must establish and agree on a provisional assessment for the
proposed operation on the basis of the guidelines referred to in MARPOL
Annex IVReg. 6.2 and m ust notify the IMO of the agreements. When the
tripartite agreements have been notified to the IMO, the agreements of
the assessments for the products (or trade names) are issued in the form of
MEPC .2/Circular.

20

Upper Explosive limit

UEL (see Flammable limits)

Upper Flammable limit

UFL (see Flammable limits)

Vapour density

(See Relative vapour density)

Vapour pressure

The pressure exerted by the vapour above the liquid at a given temperature.

Ventilation

The process of maintaining in a space an atmosphere suitable for human
access, by natural or mechanical means using a fixed or portable system.

Venting

The release of cargo vapour or inert gas from cargo tanks and
associated systems.

TANKER SAFETY GUIDE (CHEMiCAL5)


CHAPTER 1
HAZARDS AND PROPERTIES
OF CHEMICALS


1

HAZARDS AND PROPERTIES
OF CHEMICALS

This chapter gives an introduction to the range of hazards normally associated with the properties of chemicals
that are carried as cargoes, and the precautions necessary to minimise or avoid these hazards.

1.1

Introduction

1.2
1.2.1
1.2.2
1.2.3
1.2.4
1.2.5
1.2.6
1.2.7
1.2.8

Physical Properties
Density and specific gravity
Volume expansion coefficient
Melting point
Vapour pressure
Boiling point

1.3
1.3.1
1.3.2

Flammability
Flash point

1.4
1.4.1
1.4.2

Static Electricity
General
Charge accumulation and relaxation
in liquids
Generation of static
Static generation during cargo operations
Static generation during tank cleaning
Static generating portable equipment

1.4.3
1.4.4
1.4.5
1.4.6

22

Vapour density
Viscosity
Water solubility

Explosive/flammable limits

TANKER SAFETY GUIDE (CHEM,CALS)

1.5
1.5.1
1.5.2
1.5.3
1.5.4
1.5.5

Toxicity
General
Exposure to toxicity
Degrees of toxicity
Exposure limits
Precautionary principles

1.6
1.6.1
1.6.2
1.6.3
1.6.4
1.6.5
1.6.6
1.6. 7

Reactivity
General
Unstable chemicals
Chemicals that react with oxygen
Chemicals that react with water
Reaction of acids with water
Incompatible chemicals
Reaction with construction materials

1.7
1.7.1
1.7.2

Corrosive Substances
General
IBC Code requirements

1.8
1.8.1
1.8.2
1.8.3

Hazardous Cargo Information
Material Safety Data Sheet
Contents of a Material Safety Data Sheet
Inhibited cargoes


1.1

INTRODUCTION
Chemical tankers are designed and equipped to transport a wide range of different cargoes and often
carry a large number of products si multaneously. The operation of chemical carriers differs from that
of oil tankers in that, on a si ngle voyage, a large number of cargoes with different properties and
inherent hazards may be carried. In port, several products may be handled simultaneously at one
berth, typically involvi ng such different operations as loading, discharging and tank cleaning.
The transportation of bul k chemicals by sea not only requires purpose built ships and equipment,
but also seafarers who have received specialist training, both theoretical and practical, i n order
to understand the properties of the various chemicals and the potential hazards i nvolved in
cargo operations.
When planning the carriage of chemical cargoes it is essential that the ship's crew and the company
managi ng the vessel are provided with a full specification of each cargo in order to ensure compliance
with international stowage, handling and carriage requirements. Furthermore, the cargo details
should provide the ship's crew with all of the information that they may require i n order to handle th e
cargo safely and to mini mise the i mpact that cargo operations may have on the environment.

1.2

PHYSICAL PROPERTIES

1.2.1

DENSITY AND SPECIFIC GRAVITY
Den sity is defined as the mass of a substance per unit of volume, u sually expressed in the standard (SI)
unit kg/m 3.
Specific gravity (SG) is the ratio of the mass of a product when measured against the mass of an
equal volume of water. Because specific gravity is expressed as a ratio, it has no measurement
units. However, the SG can vary according to the temperature of the product. It is quite common
to see the SG quoted as 20•04·c. which refers to the density of the product at a temperature of
2o·c referenced against the den sity of water at a temperature of 4•c . This temperature reference is
selected because water has its maximum density of 1,000kg/m ' at 4•c.
For chemical carriers, design parameters specify the maxi mum density of products that can be carried
in each cargo tank. The design strength can differ between various tanks on board the same ship,
resulting in different maxi mum densities and maximum filling ratios.
The information regarding tank strengthening can be found in th e classification society's specifications
for the ship, and the Master should be familiar with any restrictions that may be imposed when
loading high density cargoes. Especially important is the need to be aware of and avoid the risk of
slack loading a tank. This is because slack loading can lead to sloshi ng forces that may cause damage
to the tank structure or its internal fittings and equipment. Classification societies provide information
about tank strength in various formats and the Master should ensure that the restrictions are
understood and that there is full compliance.

1.2.2

VOLUME EXPANSION COEFFICIENT
Whereas the mass of a product does not vary with temperat ure its volume gen erally expands with
increasing temperature. As a consequence, the density will vary with tem perature.
For petroleum products, volume correction factors are calculated using American Society for Testi ng
and Materials (ASTM) tables.

23


For chemicals, density at standard temperature (usually 2o·c ) is converted to density at the actual
temperature, usi ng the following fonmula:

Oa = Or + ((Tr - Ta) x OCF)
Where:
Oa = density at actual temperature (Ta)
Or = density at reference temperature (Tr)
OCF = density correction factorrc
Density correction factors are usually not stated in the MSDS or commodity databases, and w ill
typically be obtained from the loading master or cargo surveyor.
For example: Methanol
Dr at 2o·c = 0.7913
The OCF for methanol is 0.00092/'C
What is the density (Oa) at 35•c?
Oa = 0.7913 + ((20 - 35) x 0.00092)
Oa = 0.7775

Sufficient space must be allowed in the tank for expected expansion of cargo during the voyage
due to a rise in outside temperatures or of cargo bei ng similarly affected by heated cargoes in
adjacent tanks.
A useful formula for calculating the maximum volume of a cargo to be loaded in a tank (Vmax) is:

Vmax

= 0.98 V x (Omax/01)

Where:

1.2.3

0.98V

98% volume of the tank

Omax

Density of the cargo at the maximum expected temperature

DI

Density of the cargo at the loading temperature

MELTING POINT
The melting point of a product is the temperature at which it changes from the solid to the liquid
state. At the melting point, th e solid and liquid phases exist in equilibrium. The temperature of the
reverse process when a product changes from a liquid to a solid is referred to as the freezing point or
crystallisation poi nt. For most pure chemicals (which are products with a defined quality specification)
the melting and freezing points are approximately equal. However, some products such as vegetable
oils, creosote oil, lube oil additives and clean petroleum products, whose quality varies, do not have a
defined melting poi nt but a melti ng range.
Cargoes with a melting poi nt above the ambient tem perature of the ship's trading area will need to
be heated in order to remain liquid. The structure and equipment of a ship can impose a limitation
on the carriage of h eated cargoes, which should be documented on board. Exceeding this limitation
could damage the cargo tank coating or coati ngs in adjacent spaces such as ballast tanks. Excessive
heat will also create thermal stresses withi n the steelwork of the tank and risk structural damage.
Caution should be exercised when carrying high heat products. Cargo in non-insulated pipes and
vents may freeze. Should vent lines or vents be blocked structural damage may occur due to a
vacuum or overpressure developi ng w ithin the tank.

24

TANKER SAFETY GUIDE (CHEMICALS)


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