Approved General Manager

CHEMICAL TANKER MANUAL Date 15.02.2017

Chapter 10
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10. GAS-FREEING and TANK CLEANING PRCEDURE

Following requirements shall be followed for tank cleaning and gas freeing for Marpol Annex II cargoes. Ship’s
specific & approved P&A (Procedures and Arrangements) manual should be consulted.

10.1 General
Water is the most common washing medium or flushing the bottoms of the cargo tanks, or for cleaning cargo tanks
using tank washing machines. It’s readily available in large quantities, it’s an efficient cleaner and on most
chemical tankers the wash water can be heated when necessary. Nevertheless, it’s sometimes necessary to use
small quantities of chemicals additives or detergents as a cleaning agent in order to improve cleaning effect. Only
approved type tank cleaning detergent shall be used for tank cleaning as listed in the MEPC.2/Circ XX Cleaning
additives, annex 12. (See the latest MEPC.2/circ.XX from MILBROS). See for more details of handling
chemicals/detergents, general safety manual chptr 3.6.
However, in some situations water will not be used. Water must not be used in the case of chemicals that
dangerously react with water and a washing medium other than water may also be used for commercial reasons. It
may be permissible to use ventilation to remove cargo residues and gas free a cargo tank after a highly volatile
cargo has been carried. In every case full safety aspects of the operation should be considered.

When tank cleaning in port relevant regulations and limitations established by the port authority and terminal
should be complied with.

After carrying a low flash point cargo (flash point below 61 0C determined by the closed cup test), a flammable
vapour mixture should always be suspected until tests have established that the atmosphere is non-flammable.
Equal care is necessary after carrying a non-volatile flammable cargo at a temperature above it is flash point or
after discharge of any cargo or ballast that had been loaded into a tank that was not free of flammable vapour.
Toxic vapour in harmful concentrations should also be assumed after unloading cargoes which have a vapour
inhalation hazard. For the safety procedures detailing cleaning of a cargo tank which had contained flammable
product see TSG (C) 7.

If a cargo is being handled at a temperature within 10 C of its flashpoint, it should be considered volatile. Therefore
a cargo with a flashpoint of 80 C should be considered volatile if handled at a temperature of 70 C or above. Tank
washings shall be carried out same as low flash point cargoes which determined acc. to closed cup method.

Cargo vapour, toxic or flammable, should be suspected in cofferdams or any other spaces within the cargo area
into which such cargoes may have leaked.

All ships certified to carry noxious liquid substances in bulk shall be provided with a Procedures and Arrangements
(P&A) Manual, approved by the flag administration, which addresses the marine environmental aspects of removal
and disposal of residues from cargo tanks, and describes how to perform those operations. The Manual should be
adhered to in all respects, including the performance of mandatory pre-wash requirements in accordance with
Marpol 73/78 Annex II.

All DSM vessels are provided with Milbros Software for tank cleaning guidance. This software is automatically
updated via internet on board. Operation department has also access to this program. Program has the below
features.
From/To Tank Cleaning Recommendations Coating Resistancy (Stainless, Zinc, Epoxy)

Material Safety Data Sheets (MSDS) USCG Compatibility Groups & Exceptions

Regulatory Data (IBC Code Product Names) Heating Requirements

GESAMP Profiles Inerting/N2 Requirements

Prior Cargo Lists (FOSFA, NIOP, EU ) Safety/Emergency Information

Specifications and Cargo Handling Chemicals’ Physical Properties

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10.2 Responsibility

Chief Officer is responsible to supervise all tank cleaning and gas freeing operation. All stages of the operation
should be performed in a safe manner appropriate to each individual chemical’s physical characteristics, such as
toxicity, corrosiveness and reactivity.

All crew involved in the operation should be fully briefed by Chief Officer on the tank washing plans, and their roles
and responsibilities prior to commencement.

All other personnel on board should also be notified that tank washing is about to begin and this notification must
in particular be extended to those on board not involved directly in the tank washing operation but who, by virtue of
their own concurrent tasks, may impact upon the safety of the tank washing operation.

A written tank cleaning plan should be drawn up and made available for reference by all personnel participating in
the operations. SMS form no 3101 will be used for this purpose and to be kept ready Cargo Control Room Bulletin
board or any similar suitable place.

No Tank Cleaning should take place unless Authorised by the Master

10.3 Pre-cleaning Conference

A pre-cleaning conference under the leadership of the Chief Officer should be held prior to any tank cleaning or
gas freeing operation. Other crew members involved should be identified by the responsible officer, and their role
explained. The conference should take the opportunity to clarify that all personal involved fully understand their
duties during the forthcoming tank cleaning operation.

The conference should confirm:

 The tanks to be cleaned and the cleaning sequence.
 The type of cargo to be cleaned from each tank and its characteristics. Cargo information sheets should
be available so that personnel involved are familiar with the hazards.
 The major risks during cleaning such as toxicity, flammability, corrosiveness and reactivity.
 If the adjacent tank is loaded, loaded cargo’s flash point, transport temperature, if has additive shall be
taken account. Possible adverse effects of wash water temperature and / or steaming shall be considered
and the risks to be assessed.
 The safety equipment and personal protective equipment to be available and ready for use throughout
operation and during connecting and disconnecting of hoses at the cargo manifold.
 The cleaning instructions (plan) to be followed in each case.
 The means of disposal of any cargo residues and the contaminated cleaning water. The relevant slop tank
washing and gas freeing operations. If wash water will be sloped which tank/tanks will be used?
 The precautions necessary to confirm that the cargo deck area is free from cargo vapours during tank
washing and gas freeing operations.
 That at regular intervals throughout the operation, checks will be made to ensure that tank washing
containing cargo is not inadvertently being discharged into the sea.
 A written tank cleaning schedule should be drawn up and made available for reference of all personnel
participating in the operations.

Once the tank-cleaning plan has been approved by the Master, the Chief Officer shall hold a meeting with all
Personnel involved in the tank cleaning, briefing them about the planned tank cleaning. All personnel involved in
the cleaning operation are to sign for acknowledgement and understanding of the plan.

¶Special Note: Following should be cared during planning process.

After carriage of Methyl alcohol, Ethyl alcohol cargoes in epoxy/marineline coated tanks, the tanks should NOT be
washed with water, steamed until the tank coating has been restored to its original condition by forced
ventilation. Premature coating failure can result if coating manufacturer guidelines are not followed. ¶
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10.4 Safety Requirements

Tank cleaning is a hazardous operation which requires an increased level of safety awareness. Additional safety
precautions must include, but not be limited to the following:

 Smoking regulations must be in force as for a load or discharge port.

 All doors and windows kept closed.
 Air conditioning must be on recirculation. (intake to be partly opened to provided positive pressure inside)
 No unauthorised personnel allowed on deck.
 Other safety requirements as per the current edition of the Tanker Safety Guide Chemical (If Annex II
cargo to be carried) / ISGOTT / IMDG / MSDS.
 Characteristics of the product must be available.
 Equipment to be used must be checked and be in order.
 All portable hoses to be used must be tested in a dry condition for electrical continuity prior to the
operation.
 Personal protective equipment must be ready and used when necessary.
 Fire fighting equipment must be ready for use
 If in port or alongside berth permission from local authorities or terminal must be obtained
 A pre-cleaning conference, under the leadership of the Chief Officer should be held prior to any tank
cleaning or gas freeing operations.
 A written Tank Cleaning Schedule should be drawn up and made available for reference by all personnel
participating in the operations.
 Gas detection equipment must be in operation and suitably calibrated throughout the operations.

10.5 Preparations

Before any tank cleaning or gas freeing operations begin, the Chief Officer should confirm that all necessary
equipment is available and that adequate checks are made to establish that all equipment to be used in good
working condition. Both before and during tank cleaning and gas freeing operations, the Responsible Officer
should be satisfied that appropriate precautions are being observed. All personnel on board should be notified that
tank cleaning or gas freeing is about to begin and only those personnel involved in the operations should be
allowed into the cargo tank area.

It is especially important that the external doors remain closed, ventilation is switched to re-circulation with positive
pressure inside, and that smoking prohibition is strictly observed. No welding or any other hot work causing sparks
is to be allowed.

If other craft are alongside the tanker, their personnel should be notified that tank cleaning operations are about to
commence and their compliance with all appropriate safety measures should be confirmed.

10.6 Precautions for Gas Freeing and Tank Cleaning While Alongside

Before gas-freeing and tank cleaning are begun, the permission of the port authority and terminal operator should
be obtained and the appropriate personnel ashore should be consulted to confirm that conditions on the jetty do
not present a hazard, and to obtain agreement that operations can start.

The following checks should be made before operations commence:

 That appropriate personnel on board have been duly instructed and notified that gas freeing or tank
cleaning is about to start.
 That essential protective clothing respiratory protection equipment is being worn if so required.
 That fresh water shower and eye wash arrangements are ready for immediate use in the event of
contamination of personnel.
 That work not related to cargo operations and not otherwise essential is avoided in the cargo area during
the tank cleaning operations.
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 That cargo pipe lines serving a set of cargo tanks are isolated from the tanks to be cleaned or gas freed,
unless all tanks in that set are to be cleaned.
 That tanks served by a common vent system are properly isolated.
 Those cargo tank lids, tank washing openings, ullage openings and sighting ports in un-cleaned tanks are
kept closed until they are to be cleaned.
 That all sea and overboard discharge valves connected to the cargo and ballast systems are shut and
secured when not in use.
 That permission guaranteed to tank cleaning alongside involving transfer of washing ashore, shore
representatives should be advised of the nature of all grades in the previous cargo.
 Those pumproom (Cargo Pumproom) precautions are being observed and will continue to be observed
throughout tank cleaning and gas freeing operations.
 That fire fighting equipment is ready for immediate use.
 Scuppers are properly plugged, and spill pans or trays are in place beneath the manifold connections
 No unauthorized craft is alongside, and authorized crafts that are alongside are warned that cleaning is
about to begin.
 Any necessary hose connections to shore or craft alongside are properly made and supported

10.7 Tank Washing Atmospheres

Tanks washing may be carried out in one of the following atmospheres;

Inert: an atmosphere made incapable of burning by the introduction of inert gas and the resultant reduction
of the overall oxygen content. The oxygen content of the tank atmosphere should not exceed 8% by
volume.

Non inerted: an atmosphere which is undefined. (may be above, below or within the flammable range)

10.8 Precautions when tank washing in an inert atmosphere

Although the atmosphere in a properly inerted tank is incapable of burning, the following precautions should be
observed:

• When portable washing machines are used, all hose connections should be made up before the washing
machine is introduced into the tank. Connections should not be broken until after the machine has been
removed from the tank. However, to allow draining of a hose, a coupling may be partially opened and then
re-tightened before the machine is removed.

• The tank should be kept drained during washing. Washing should be stopped to clear any build up of wash
water.

When there is a need to maintain an inert atmosphere during tank washing, the following points should be
observed.

• The purity and pressure of the inert gas being delivered during the washing process should be monitored.

• Before each tank is washed, the oxygen level in the tank should be determined both at a point about 1 metre
below the deck and at the middle level of the ullage space. At neither location should the oxygen level
exceed 8% by volume. Where tanks have a complete or partial swash bulkhead, the measurement should
be taken from similar levels in each section of the tank. The oxygen content and pressure of the inert gas
being delivered during the washing process should be continuously recorded.

• If during washing, the oxygen level exceeds 8% by volume or the pressure of the atmosphere in the tank is
no longer positive, washing should be stopped until satisfactory conditions are restored.

• During tank washing operations, measures must be taken to verify that the atmosphere in the tank remains
non-flammable (oxygen content not to exceed 8% by volume) and at a positive pressure.
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Some cargoes which are not flammable are carried under inert blanket for cargo quality reasons. In this case,
gradual decay of the inert atmosphere during cleaning is acceptable. In all other cases, if the inert atmosphere is
not maintained then the procedures used and safety precautions taken should be as for an undefined atmosphere.

10.9 Precautions when Tank Washing in an Undefined Atmosphere (Non Inerted)

On most of the chemical tankers, tank cleaning is carried out in a non inerted atmosphere. Non-inert cargo tank
washing should only be undertaken when both the source of ignition and the flammability of the tank atmosphere
are controlled. To achieve this, the following precautions to control “sources of ignition” and “fuel” MUST be taken
for tank washing operations in a non-inert atmosphere condition. The procedure for cleaning cargo tanks after
discharge of volatile flammable liquid is given below – Ref TSG (C) Section 7.3.4

Good tanker practice will avoid all normal sources but, in addition, the following precautions should be taken even
the risk from static electricity is eliminated:

 Before Washing the tank bottom should be flushed with water, so that all parts are covered, and then

stripped. The piping system including cargo pumps, crossovers and discharging lines should also flushed
with water. The flushing water should be drained to the tank designated to receive slops. This operation
may not be necessary if the ship is fitted with an efficient stripping system and the cargo tank and pump
line have been stripped as detailed in ship’s P&A manual.

If cargoes are highly water reactive this operation must not be carried out

 When portable washing machines are used, all hoses connections should be made up before the washing
machine is introduced into the tank. Connections should not to be broken until after the machine has been
removed from the tank. However, to allow draining of a hose, a coupling maybe partially opened and then
re-tightened before the machine is removed from the tank.

 Ropes made of synthetic fibres should not be used to support tank cleaning machines.

 No machine may have a throughput greater than 60 m per hour and no nozzle may have a throughput
3

greater than 17.5 m per hour.

3

 The total water throughput per cargo tank should be kept as low as practicable and must in no case
exceed 110 m per hour.
3

 The tank should be kept drained during washing. Washing should be stopped to clear any build-up of
wash water.

 Re-circulated wash water should not be used, because it may increase the generation of static electricity.

 Sounding rods and other equipment must be introduced through a sounding pipe reaching close to the
bottom of the tank and earthed to it. If a sounding pipe is not used then the additional precautions related
part of this chapter should be followed.

 No other material that may create a spark or static electricity should be lowered into the tank.

 Steam should not be injected into the tank

10.10 Washing After a Low Flash Cargo

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After discharging a low flash point cargo (flash point below 60’C), the tank bottom should be flushed with water and
then stripped. The bottom flush should be undertaken using the main cargo pumps and lines.
The piping system, including cargo pumps, crossovers and discharge lines, should also be flushed with water. The
flushing water should be drained to the tank designated to receive slops. This option may not be necessary if the
ship is fitted with an efficient stripping system, and the cargo tanks and pipelines have been stripped as detailed in
the ship’s P & A manual.

If the last cargo is not miscible in the water and density less than 1 gr/cbm the cargo will locate above the water
and bottom flushing may not be effective. In this case use of sounding pipe may be more effective (continuous
pumping at the same time)

The tank should be ventilated to reduce the gas concentration of the atmosphere to 10% or less of the Lower
Flammable Limit (LFL). Gas tests must be made at various levels and due consideration should be given to the
possible existence of pockets of flammable gas, in particular in the vicinity of potential sources of ignition such as
mechanical equipment that might generate hot spots, e.g. moving parts such as found in in-tank (submerged)
cargo pump impellors

Tank washing may only commence once the tank atmosphere reaches 10% or less of the LFL

10.11 During Washing

Atmosphere testing should be done after first washing cycle and taken at various levels inside the tank during
washing to monitor the change in LFL percentage. Consideration should be given to the possible effect of water on
the efficiency of the gas measuring equipment and therefore to suspension of washing to take readings.

During washing if the gas concentration is higher than 35% of the LFL, washing MUST be stopped and only
resumed when continued ventilation has reduced gas concentration to 10% or less of the LFL, one more
atmosphere test after next washing cycle must be performed.

Mechanical ventilation should, whenever possible, be continued during washing and to provide a free flow of air
from one end of the tank to the other.

If the tank has a venting system that is common to other tanks, the tank must be isolated to prevent ingress of gas
from other tanks

10.12 Precautions for Sounding Tanks When not Using a Sounding Pipe

If a sounding pipe is not used, it is essential that any metallic components of the sounding rod or other equipment
are bonded and securely earthed until removal from the tank. This precaution should be observed during washing
and for five hours afterwards, unless the tank is continuously mechanically ventilated after washing, in which case
the delay period can be reduced to one hour.

During the delay period:

 An interface detector of metallic construction may be used if earthed to the ship by means of a clamp or
bolted metal lug.
 A metal rod may be used on the end of a metal tape which is earthed to the ship.
 A metal sounding rod suspended on a natural fibre rope should not be used even if the end at deck level is
fastened to the ship, because the rope cannot be completely relied upon to act as an earthing path.
 Equipment made entirely of non-metallic materials may in general be used: e.g. a wooden sounding rod or
float may be suspended on a rope without earthing.
 Neither ropes made of synthetic polymers nor chains, should be used for lowering equipment into cargo
tanks.

10.13 Steaming of Cargo Tanks

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Because of the hazard from static electricity, steam should not be introduced into cargo tanks where there is a risk
of the presence of a flammable atmosphere. It should be borne in mind that a non-flammable atmosphere cannot be
guaranteed in all cases where steaming might be thought to be useful.

The tank subject to steaming may be adjacent to tank which contain heat resistance cargo and/or polymer cargo.
In that case, steam introduce can cause fire and polymerization. Therefore, adjacent tanks cargoes should be
checked before commenced steaming and, if there is any adjacent cargo tank which contain heat resistance
and/or polymer cargo, steaming should NOT be done.

Steaming can produce mist clouds, which may be electrostatically charged. The effects and possible hazards from
such clouds are similar to those described for the mists created by water washing, but levels of charging are much
higher. The time required to reach maximum charge levels is also very much less. Furthermore, although a tank
may be almost free of a hydrocarbon gas at the start of steaming, the heat and disturbance will often release
gases, and pockets of flammability may build-up.

Toluene steaming and/or ‘steaming’ with any chemical/solvents, for tank cleaning purpose, is strictly
prohibited

10.14 Free Fall of Wash Water in the Slop Tanks

It is essential to avoid the free fall of water or slops in to the tank. In order to avoid splashing, the liquid level must
always exceed the discharge inlets in the slop tank minimum one meter as depth. It is not necessary, when the
slop and cargo tanks are fully inert completely.

10.15 Special Cleaning Methods

Water washing may be inadequate or inappropriate after the carriage of certain products, because tank can only
be adequately cleaned by special cleaning methods or cleaning agents. Where it is decided to use special
cleaning method by the master and the Company, and well documented experience indicates that it is safe to do
so, through company guidance should be provided that describes the procedures for the ship to follow.

Where a special cleaning method is to be used in port, local authorities may impose additional safety or
environmental requirements. Therefore, local authorities should be informed accordingly in advance and
permission should be guaranteed before commence.

Some cargoes may react with certain cleaning agents and produce large amount of toxic or flammable vapours, or
render equipment such as pump inoperable. The choice of a tank cleaning agent should be made with full
knowledge of the cargo characteristic. In any doubt, the company should be informed and asked for further
information.

If a special method involving cleaning agents is to be used, it may create an additional hazard for the crew. All
crew should be trained, and protected from, the health hazard associated with such a method. The cleaning
agents may be added to the wash water or used alone. The cleaning procedures adopted should not entail the
need for personnel to enter the tank.

If, however, the only practical means of cleaning involves personnel entering the tank then the precautions set out
in chapter Hand Spraying parts should be strictly followed.
No one should enter any cargo tank unless express permission to do so has been received from the responsible
officer, and all appropriate precautions taken. The tank atmosphere should be safe for entry and an entry permit
issued. Chemical absorption detectors should be used for detecting the presence of specific gases and vapours at
TLV levels.

10.16 Arrangements for Disposal of Tank washings, Slops and Dirty Ballast

10.16.1 General
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During normal operations of a chemical carrier, the main need to dispose of chemical residues, slops or water
contaminated with cargo will arise during or immediately after tank cleaning. Final disposal of slops or wash water
should be in accordance with the ship's P&A Manual. Tank washings and slops may be retained on board in a slop
tank, or discharged ashore or into barges.

Mixing of ANNEX-I and ANNEX-II slop is strictly prohibited.

The use of Annex 1 products for tank cleaning of Annex 2 is subject to company approval.

Where required, if any Annex I product to be used for washing Annex II cargo tanks, the washing water
and, the cargo tanks (further washings) shall be treated according to Annex I regulations
10.16.2 Mandatory Pre-wash Water for Marpol Annex II Cargoes
Following discharge of Category X substances or highly viscous or solidifying Category 'Y’ substances the tanks
previously containing this cargo should be prewashed before the vessel leaves port in accordance with the P&A
Manual. A receipt for the disposed slops must be received and appropriate entries must be made in the cargo
record book.

Mandatory pre-wash procedures should be conducted strictly in accordance with ship’s P&A Manual and the
resulting contaminated wash water should always be discharged to reception facility. The intention of MARPOL is
that this should happen immediately following the cargo discharge operations, and in the same port. However,
occasions do arise when adequate shore reception facilities for the washing are not provided and the ship must
retain the washings on board until arrival at another port. Marpol addresses this matter, and the P&A Manual will
provide guidance on the correct procedures for a particular ship. During such a voyage, the slops and tank
washing should be given same safety and environmental care as the original cargo.

If there is any doubt or ambiguity as to the Pollution Category of the cargo, the Company must be
contacted immediately before any operations commence for guidance and further instructions.

10.16.3 Dirty ballast

Dirty ballast, caused by ballasting into a cargo tank before the tank is cleaned, should be treated as slops, and
must be disposed of in accordance with MARPOL and the ship's P&A Manual

10.16.4 Safety Precautions during Discharge of Cargo Slops into the Sea (Marpol Annex II cargoes only)

When discharge overboard is permitted, it should only be undertaken when;

 The ship is at sea and proceeding en route at a speed of at least 7 knots and
 The discharge is made below the waterline through the underwater discharge outlet not exceeding the
maximum rate for which the underwater discharge outlet is designed and
 At least 12 miles off-shore from the nearest land and in a depth of water not less than 25 meters.

See Marpol Annex II, Chapter I, for en route, nearest land and depth of water definitions.
Antarctic Area: The sea area south of latitude 60 0 S. In the Antarctic area any discharge into the sea of noxious
liquid substance (Marpol Annex II) or mixtures containing such substances is prohibited.

Discharge of chemical residues should normally be below the waterline through an underwater discharge outlet on
the side of the ship away from essential water inlet valves. Discharge rate of wash water can be restricted due to
diameter of underwater discharge outlet and therefore the ship’s P&A Manual should be consulted for rate. In the
interests of safety, this procedure should be adopted even when it is not a mandatory requirement.

The company requires that all operations with Annex II cargoes, dirty ballast and slops on board the vessel are
made in accordance with the appropriate legislation. Each stage of such operations to be properly recorded in
Cargo Record Book as required by MARPOL 73/78 amended.

Chapter 10.4 "Safety Requirements" of this manual should be considered. Additional to chapter 10.4, Following
safety precautions should be complied when discharging washing water or slop to the sea:
- Chief Engineer should be advised 1 hour before commence the discharging,
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- Both Engine Room and Ballast Sea Chest valves on the discharging side should be CLOSED and only sea
chests on the other side should be used during the discharge, if Under water discharge line fitted on starboard
side, port side sea chest suction should be used.
- Evaporator should not be used when discharging Toxic chemicals washing residues.

10.16.5 Interpretation of "En-Route" definition and Local Regulation on Tank Cleaning Operation at Sea

As per article 3.1 of Unified Interpretation of the Annex II of the Marpol Convention, the “en route” definition is as
follows:

"Enroute" means that; . the ship is  underway at sea on a course or courses, including deviation from the
shortest direct route, which, as far as practicable for navigation purposes, will cause any discharge to be spread
over as great an area of the sea as is reasonable and practicable.

Under and consistent with the international Law, each state has the prerogative to add any additional measures in
order to protect its environment and its particular ecosystem as such the vessel shall comply with any regional
rules of that State.

Some countries local regulations may consider from port " A" to port "A", is NOT a Voyage therefore don't allow
the return of vessel to same port after discharging of tank cleaning water.

Due to variety of interpretations of the “en route” definition, , the Master shall obtain precise information from the
agent about the interpretation of the Marpol regulations made by the local authorities, When the vessel is subject
to leave from port "A" for discharging of tank cleaning water to sea and return to port "A" again.

In such cases, Master shall immediately inform the DSM and commercial operator. A vessel can only leave from
port for the sole purpose to discharge of tank cleaning water to sea if this permission obtained from the local
authority.

If there is no permission of Local Authority, in the cases tank washing residue shall be transferred to a shore
facility or in to a barge

10.16.6 Management of Slop Tanks

Compatibility of various cargo and cleaning chemicals should be considered just as carefully when handling slops
as when handling the cargoes themselves. Particular care is needed when washing several tanks which have
contained dissimilar cargoes, and compatibility should be taken into account when selecting the destination tank
for stripped wash water. The following should be avoided:

• Mixing of slops from Annex I (oil) cargoes with slops from Annex II (chemical) cargoes.
• Mixing of slops from incompatible cargoes.
• Mixing of slops from vegetable oils or fats with chemical slops or petroleum oil slops.

If the ship's cargo tanks are used as slop tanks, care should be taken to avoid introducing slops from cargoes
which are incompatible with the tank coating. In this regard, some cargoes which are they compatible may, when
mixed with water, form acids and thus damage a coating, e.g. slops from hydrolytic cargoes in a zinc coated tank.

10.16.7 Chemical Washing (Washing with Tank Cleaning Detergent)

Due to the very stringent cleaning requirements in the chemical trade, it is a very common practice to use various
types of cleaning detergents to prepare the cargo tanks for next cargo. The detergent manufacturers generally
provide detailed product data information including the applications, their recommended dosages etc. These
should be used as a guide to plan the chemical (detergent) cleaning operation. It is possible for certain chemicals
to adversely affect the tank coatings; hence their compatibility with various coatings should be established before
carrying out chemical cleaning.
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Only approved type tank cleaning detergent shall be used for tank cleaning as listed in the MEPC.2/circ XX (Last
Update List In Milbros )

The crew in charge of tank cleaning operation should be aware of possible health hazards associated with
use of tank cleaning chemicals / detergents, which may have a low TLV.

Due to tank cleaning chemicals/detergents act as electrostatic generators, to use cleaning chemicals are
NOT ALLOWED in flammable condition. (They may only be used in inerted tanks or gas free tanks)

Tank cleaning chemicals may be used in below methods;

A) ¶Tank Cleaning Detergent Recirculation

This is the most commonly used method  and perhaps most effective when preparing cargo tanks to wall wash
standards. The following procedure is recommended when carrying out detergent cleaning using recirculation
method:

• Identify the chemical that will be used along with the desired concentration, if any heating requirement
• Always preferable to prepare the chemical solution in freshwater
• Check for compatibility with tank coating
• Plan the duration of the chemical recirculation along with the number and location of the machines ¶

B) ¶Tank Cleaning Detergent Injection

This is another method of cleaning when using tank cleaning detergent. The cleaning detergent is injected in to the
tank cleaning system during the main cleaning process. Similar considerations need to be given as for recirculation
as described below when preparing for injection.
• The availability of a high pressure pump to inject the detergent along with the associated fittings and
arrangements or any other arrangement specific to the vessel
• The type of detergent required and the concentration/quantity which should be injected
• The duration of cleaning
• The advantage with injecting the detergents is that there is a reduction of tank cleaning time, however it will
require large quantities of detergents as also the cleaning may not be uniform leading to improper cleaning of the
tank. Fair amount of experience is required to carry out injection of the detergent. Biggest disadvantage is, if the
tank is required to be re-cleaned, the vessel may not have adequate detergent ROB. ¶

C) Hand Spraying

The manual spraying of diluted or undiluted SOLVENTs onto the tank wall, included but not limited most
commonly used being Butlylglycolether, Methanol or Acetone (in hot climates diluted with water to reduce
volatility) or a Methanol/Acetone 50/50 mixture is STRICTLY PROHIBITED. Also the use of Toluene is strictly
forbidden in this case because of the explosion risk due to electrostatic discharge.

Hand spraying is typically done to correct unsatisfactory cleaning results manually, which have been identified
after inspection of the tank. Only demi water (De-Ionized water) and detergents (refer to their manufacturer’s
instructions and MSDS) can be used for tank cleaning purpose. Where operations of this nature have to be carried
out, it is mandatory the Enclosed Space Entry Procedures (see chapter 8.3) are strictly adhered to and that full
protective suits and self-contained breathing apparatus are worn by personnel engaged in such operations due
to the exposure risks when using detergents. The crew are to be thoroughly briefed on possible safety hazards
and the safety precautions to be taken during the cleaning.
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Where it is decided that such an operation is necessary, a risk assessment should be carried out and a safe
system of work developed. Using of No-name products, unknown detergents and detergents which are not
suitable for spraying is STRICTLY PROHIBITED.

D) Local Tank Cleaning by Brushing and Wipe the Tank Surface

Under some circumstances brushing or wiping of cargo tanks may be necessary. In such conditions ıt should be
considered that use of chemicals may be hazardous for personal safety.
-Helmet, Googles, Chemical resistant boots, Chemical gloves, and splash type suit MUST be worn.
-Do not manually use chemicals which contain any Solvent. Solvents are harmful for breathing system and eyes.
-Do not manually use aggressive corrosive cleaning chemicals which contain Caustic, Acid, Phosphate, Calcium
and Fleur. These aggressive chemicals only may be used for closed (circulating/injecting) cleaning methods. Such
chemicals are harmful for skin and eyes.
-Only light detergents which suitable for manual washing may be used for brushing and wiping. Above mentioned
PPE should be used when using subject light detergents.
MSDS of On-board tank cleaning detergents/chemicals should be checked to categorise as per application
methods. Suitable detergents for manual use (brush/wipe) should be marked as “SUITABLE FOR MANUAL USE”.
All other chemicals and detergents should be marked “ONLY FOR CLOSED WASHING. DO NOT USE FOR
BRUSHING/WIPING”” Markings should be in crew mother language for easy understanding.

10.16.8 Washing of Water Reactive Cargoes

Following chemicals are water reactive and their washings require special attention;
- Sulphuric acid
- Nitric Acid
- Chlorosulphonic Acid
- Chloropropionic Acid
- Oleum
- Nitrating Acid ( mixture of Sulphuric Acid and Nitric Acid)

Above mentioned products are highly corrosive and also highly reactive with water. Therefore bottom flushing for
these products cleaning is strictly prohibited. Personnel in charge should be worn gas tight chemical suit and SCBA
during washing. Their reaction with water is produce heat and toxic fume.

At the end of discharging tanks, pumps and lines should be well stripped and pump out to the shore. Remain
quantity in the tank should be kept as much as minimum.

Plenty of water (as much as possible) should be given to the tank via butterworth machines when commence
washing and tank pump should be started simultaneously. Vessel should be well trimmed (as advised in P&A
Manual) so, wash water will be drained to pump well. Pump rate should be so arrange that washing water should be
disposed simultaneously and bottom of the tank should be kept empty. Do not stop washing before 30 minutes after
commence washing and do not open any drain valve before line flushing. Tank hatches should be kept closed
during washing. Related hatches can only be open when introducing butterworth machines to the tank if there is no
fix butterworth system in the tank.

Wash water should be disposed to sea directly if cargo pollution category, vessel position and speed permits to do
so refer to Marpol. If wash water needed to be sloped, slop tanks must be filled with water at least one meter and
product quantity should be kept less than 2 % in the slop tank.

Below listed chemicals produces carbon dioxide and asphyxiant gas if react with water;
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- Toluene Diisocyanate (TDI)

- Diphenylmethane Diisocyanate (MDI, Methylenediphenyl diisocyanate)

Above mentioned products are highly toxic and produce toxic gases if react with water. Special procedure as below
should be followed.

10.16.9 Pickling and Passivation

Stainless Steel can corrode in service if there is contamination of the surface. Both pickling and passivation are
chemical treatments applied to the surface of stainless steel to remove contaminants and assist in the formation of
a continuous chromium oxide passive film. Pickling and passivation are both acid treatments and neither will
remove grease of oil. If the stainless steel is dirty it may be necessary to use a detergent or alkaline cleaner
before commencing pickling or passivation.

Stainless steel surfaces of chemical tankers should be checked regularly for an intact passive film, this can be
done using a Palladium Chloride Test Kit or, if tank walls are discolored or show rust stains, it may also be
necessary to carry out a pickling operation or passivation.

Both pickling and passivation use strong acids and it is essential when using these procedures that the MSDS
and product packaging is consulted and appropriate PPE is worn.

Be aware that Stainless pickling acids are highly corrosive to carbon steel.
It is essential that all acids are thoroughly removed by rinsing the component after completing the process as
any residual hydrofluoric acid will initiate pitting corrosion.

10.16.10 Cleaning Coated Tanks

Guidelines issued by the coating manufacturer must be consulted prior to any cleaning as the coating may
require time to cure after discharge and prior to adding any water to the tank.

When tank cleaning coated tanks the temperature of the washing water must not exceed the paint manufacturer’s
guidelines as damage to the coatings may result.

The P&A Manual must always be consulted in respect of this.

10.16.11 Gas Freeing

It is generally recognised that tank cleaning and gas freeing is the most hazardous period of tanker operations.
This is true whether washing for cleaning, gas freeing for entry or gas freeing for hot work. The additional risk from
the toxic effect of chemical gas during this period cannot be over emphasised and must be impressed on all
concerned. It is therefore essential that the greatest possible care is exercised in all operations connected with
tank cleaning and gas freeing. Chief Officer should take all necessary considerations into account when deciding if
a space is sufficiently free of vapour for any particular purpose.

The following recommendations applied to cargo tank gas freeing in general. The IBC code contains advice about
cargo tank gas freeing in Chapter 8.

It is essential to know what type of vapours can be expected: they may be flammable and/or toxic and/or corrosive:

 Venting of toxic and flammable gas during gas freeing should be through the vessel’s approved gas
freeing outlets and therefore the exit velocity should be sufficient to carry the vapours clear of the deck. No
escape of cargo vapours should occur at deck level before the concentration within the tank has fallen
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below 30% LFL and the relevant TLV. Thereafter, final clearance of the vapour mixture may continue at
tank deck level through other larger deck openings.
 If portable ventilation equipment is to be used to blow air into a tank, tank openings should be kept closed
until work on that tank is about to commence.
 Where cargo tanks are gas freed by means of permanently installed fans, air is introduced into the cargo
tank through the cargo lines. The entire line system should be thoroughly drained before venting to avoid
any obstruction of the air flow or tendency for water or cargo residues to be blown into a cargo tank.
Valves on the systems, other than those required for ventilation, should be closed and secured. The fans
should normally be blanked or disconnected from the cargo tank system when not in use.
 Fixed gas freeing equipment should not be used for gas freeing of a tank while simultaneously being used
to ventilate another tank in which washing is in progress, regardless of the capacity of the equipment.
 Portable fans should only be used if they are water driven, or hydraulically or pneumatically driven. Their
construction materials should be such that no hazard of incendiary sparking arises if, for any reason, the
impeller touches the inside of the casing. The manufacturer’s recommendations for maintenance should
be followed. Guards should be in place to prevent accidental contact with fan blades.
 Portable fans, where used, should be placed in such positions and the ventilation openings so arranged
that all parts of the tank being ventilated are effectively and equally gas freed. Fans should generally be as
remote as possible from the ventilation outlets.
 Portable fans should be so connected to the deck that an effective electrical bond exists between the fan
and the deck.
 The wind direction may cause cargo vapours to pass near to air intakes for accommodation space or
engine room ventilation and necessitate additional precautions. Central air conditioning or mechanical
ventilation system intakes should be adjusted to prevent the entry of gas, if possible by using recirculation
of air within the space.
 If at any time it is suspected that gas is being drawn into the accommodation block, the central air
conditioning and any mechanical ventilating systems should be stopped and the intakes covered or
closed. If there is any window type air conditioning system, equipment should be electrically disconnected
and any external vent or intakes closed.
 If the tanks are connected by a common venting system, each tank should be isolated to prevent the
transfer of gas to or from other tanks.
 When a tank appears to have been gas freed and on mechanical ventilation has been stopped, a period of
about 10 minutes should elapsed before taking final gas measurements. This allows relatively stable
conditions to develop within the tank space. Tests should then be made at several levels and where the
tank is sub-divided by a wash bulkhead, in each compartment of the tank. In large compartments such
tests should be made at widely separate positions. If satisfactory gas readings are not obtained, the tank
should be checked for cargo residues and then ventilation resumed.
 On completion of all gas freeing and tank washing, the gas venting system should be carefully checked,
particular attention being paid to the efficient working of the PV (Pressure Vacuum) valves and any High
Velocity vent valves. If the valves or vent risers are fitted with devices designed to prevent passage of
flame, this should also be checked and cleaned if found necessary. Gas vent rises and their drains should
be checked to ensure that they are free of any blockage.
 On completion of gas freeing, attention should be given to all equipment that has been used and to
enclosed or partially enclosed space that can retain or contain cargo residues or vapours, so that no
unsuspected dangerous pockets can remain. Places where such cargo traces may exist include cargo
lines, cargo valves, cargo pumps, stripping lines and valves, venting lines and PV valves, vapour return
lines, ullaging or sounding arrangements, heating coils, cargo handling equipment store room, protective
clothing store room and cargo sample store rooms.

10.16.11.1 Ventilation Procedure

Refer to Marpol Annex II, Ventilation Procedure approved by Administration may be used to remove cargo
residues from a tank. Any water subsequently introduced into the tank shall be regarded as clean and shall not be
subject to discharge requirements in the Marpol Annex II. Vessel capability for ventilation procedure for the
purpose of tank cleaning should be consulted in the approved ship’s specific P&A Manual. If the vessel is not
approved for ventilation of cargo residues, vessel should follow normal tank cleaning procedures. If the vessel is
capable and approved for ventilation procedure for tank cleaning purpose, cargo residues of substance with a
vapour pressure greater than 5 kPa at 200 C may be removed from a cargo tank by ventilation.
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Before residues of noxious liquid substance are ventilated from a tank, safety hazards relating to cargo
flammability and toxicity should be bear in mind. IBC Code Chapter 8 and ICS Tanker Safety Guide Chemical
should be consulted.

The arrangements for ventilation cargo tanks used for cargoes other than those for which open venting is
permitted in IBC Code should be such as to minimize the hazards due to the dispersal of flammable or toxic
vapours in the atmosphere and to flammable or toxic vapour mixtures in a cargo tank. Accordingly, ventilation
operations should be carried out such that vapour is initially discharged;
 Through the PV valves; or
 Though outlets at least 2 m above the cargo tank deck level with a vertical exit velocity of at least 30 m/s
maintained during the ventilation; or
 Though outlets at least 2 m above the cargo tank deck level with a vertical exit velocity of at least 20 m/s
which are protected by suitable devices to prevent the passage of flame.
The above mentioned outlets other than PV pipes can be fixed or portable pipes.
Atmosphere test should be performed at the outlet till to flammable concentration has been reduced to 30% of the
LFL. When the flammable vapour concentration at the outlets has been reduced to 30% of the lower flammable
limit and in the case of a toxic product, the vapour concentration does not present a significant health hazard (gas
concentration lower than TLV), ventilation may thereafter be continued at cargo tank deck level.

If the ship is in Port, permission of the port authority and if alongside in additional permission of the terminal
operator should be obtained and the appropriate personnel ashore should be consulted to confirm that conditions
on the jetty do not present a hazard, and to obtain agreement that operations can start.

The procedures for ventilation of cargo residues from a tank are as follows:
 The pipelines shall be drained and further cleared of liquid by means of ventilation equipment;
 The list and trim shall be adjusted to minimum levels possible so that evaporation of residues in the tank is
enhanced;
 If the vessel has permanently installed fan, air is introduced into the cargo tank through the cargo lines. If
not, portable ventilation equipment producing an air jet which can reach the tank bottom shall be used;
(See Marpol Annex II, Appendix 7 for the requirement)
 If portable ventilation equipment is in use, it should be placed in the tank opening closet to the tank sump
or suction point;
 Ventilation equipment should, when practicable, be positioned so that air jet is directed at the tank sump or
suction point and impingement of the air jet on tank structural members is to be avoided as much as
possible;
 Ventilation shall continue until no visible remains of liquid can be observed in the tank. This shall be
verified by a visual examination or an equivalent method.
 Gas freeing part of this chapter should be consulted for general precautions.
In all circumstances, all precautions listed in General safety Section chapter 12.2 of this manual for
enclosed space entry should be observed before any tank entry permitted.

10.16.11.2 Opening up of Cargo Lines and Handling Equipment

Cargo pipelines, manifold crossovers, vent lines etc. should be cleared of cargo residues, and should be cleaned
and gas freed at the same time as the cleaning and gas freeing of the cargo tank.

It should always be suspected, even after spaces have been cleaned and made gas free, that some cargo liquid or
vapour or both will be released whenever pumps, cargo lines valves, heating coil, etc. are opened up. Re-cleaning
and further gas freeing may be required. Precautions should be taken against the effect of such release.

If it becomes necessary to open up cargo lines and handling equipment on deck or in a cargo tank or a cargo
pump room, the following precautions should be taken:

 The task should be assessed and approved by responsible officer and a work permit issued before
starting any work.
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 After gas freeing the space, the equipment and associated pipeline should be isolated as far as possible
and further ventilated.
 After ventilation is considered to be complete, the atmosphere should be tested to confirm that its
flammability as a percentage of LFL and its toxicity relative to TLV, are within safe limits.
 When opening up, air measurements for flammable and toxic vapours should be made in the vicinity of
the working area.
 Fire fighting equipment should be ready for immediate use.

10.17 Testing of Cargo Tanks

Following criteria must be met with when deciding if a tank has been cleaned to ‘Water White Standard’:

- No traces / discolouration of previous cargo in cargo tank or line

- No odour
- No loose scale, blisters
- No free-water or condensation
- Clean cargo pump, piping and vent lines

10.17.1 Wall Wash Test

The wall-wash test is done to determine the state of cleanliness of the cargo tanks. It is usually done towards the
final stages of tank cleaning and once again after the tanks are ready.
Each vessel shall be equipped with standard wall wash test kit.

10.17.2 Wall Wash Test Procedure

The person in charge must ensure that enclosed space entry procedures followed, cargo tank has been dried and
the crew entering cargo tanks are wearing shoe covers and vinyl gloves. Prior taking sample, funnel and Nessler
tubes must be cleaned to avoid external contamination.

1. Test kits for Wall Wash test have to be stowed in closed bag or wooden box not to drop test kits into the
tank when going in and coming out of tank.
2. Put the shoe covers and wear fresh vinyl gloves.
3. Before taking sample, wash Funnel by methanol.
4. Tank samples from four parts of Fore/Aft/Port/Starboard bulkheads and in the area of 1 meter x 30cm in
width at the position of 1.5 meter from the bottom by methanol wash on the wall.
5. It is desirable to take sample from reasonable areas but don’t take sample from nook corner which can not
count as standard value.
6. During the WWT, take care that no sweat, saliva or water falls into the sampling bottle or on the funnel.
Remember that cleanliness and care during sampling are vital to ensure proper results.

10.17.3 Hydrocarbon Test

1. Fill up 60cc of Wall wash sample into 100cc Nessler tube and add 40cc of Distilled water
2. The mixture is shaken and allowed to stand for 20 minutes
3. For avoiding any observational error or for checking purity of reagent, make a standard solution by pure
methanol 50cc + distilled water 50cc and compare with sample on the black plate.
4. If the sample is very clear as standard solution of Zero PPM, it means zero PPM.
5. Analysis of the hydrocarbon test:

Sample Appearance Hydrocarbon content

Nearly clear 0.5 ppm
Little cloudy 1 ppm
Moderately cloudy 5 ppm
Milky More than 10 ppm
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10.17.4 Chloride Test

Certain cargoes are very sensitive to chloride contamination in particular glycols, methanol, ethanol .As mentioned
before the tanks should be finally washed with fresh water. However, chlorides (salt) mat still be present and a
check might be useful. The greatest risk for salt deposits is on horizontal surfaces
About one m2 of a suspected tank wall is cleaned by means of cotton wool and distilled water. The water is filtered
through a funnel into a test tube. The tube is then filled to a total volume of 100 cc with distilled water and well
mixed. Another reference test tube is filled with 100 cc of distilled water. To both tubes are then added 5 drops of
silver nitrate solution and the tubes well shaken .If chloride are present the sample tube will show a milky
appearance. To the reference tube is then added a standard (known) chloride solution in small amounts by means
of a pipette until turbidity is the same in both test tubes. With a known chloride contents in the standard solution
and a known added amount one can calculate how many grams of chlorides were present on the one m2 of the
tank wall. The total amount of chlorides in the tank can thus be evaluated. This amount divided with the tank
tonnage gives an idea of increase of chloride contents. (If no other sources of contamination occur during the
voyage). If the test tubes turn out to be too milky for comparison (which means a concentration of above some 100
ppm) its contents can be diluted with a known amount of distilled water and the calculation corrected
correspondingly.

As an example it can be noted that some specification allow 0.3 ppm of total chlorides contamination (ethanol).
This corresponds to 0.3 kg. In 1000 tons of products. The permitted increase during transportation is only a
fraction thereof. A similar method is used for the determination of chlorides in clear water-soluble products, such
as alcohols. To 50 cc of distilled water is added a few drops of nitric acid (HNO3) and 2 cc of saturated silver
nitrate solutions, then mixed with 50 cc of the product to be tested, e.g. Methanol.
A milky appearance indicates that chloride is present. Reference tests have to be carried out with the same
product with known contents of chlorides if exact values of contamination are needed.

10.17.5 Permanganate Time Test (PTT)

The purpose of this test is to detect presence of oxidizable materials. Substances reacting with potassium
Permanganate in neutral solutions reduce it to manganese dioxide that colours the solution yellow. In the
permanganate test the time required for the test solution to that of a standard solution, is measured. The colour of
the test solution changes from pink-orange to yellow-orange

Permanganate Time Test procedure is as below:

1. Fill up Sample/50cc and add 0.02% KMnO4(2cc) into 100cc Nessler tube (Sample).
2. Fill up Methanol/50cc and add 0,02% KMnO4 into another 100cc Nessler tube (Standard).
3. The mixture is shaken and then wait until the colour of violet turned orange.
4. The times required for PTT are as follows:

About 50 Minutes over at 15 C or 30 minutes over at 25 C, or 20 minutes over at 28 C.

10.17.6 PH value Test (acidity)

A neutral solution is defined as pH=7. Acidosis solutions have pH lower than 7 and alkaline solutions higher than 7
(max 14).

Water-soluble products are readily tested by means of litmus paper where a colour chance directly indicates the
pH -value roughly. There are also electrode-meters available where the pH -value can be read directly from a
scale.

The pH -value can also be established by means of neutralization with a sodium hydroxide (caustic soda) solution
from which the acidy can be calculated from the amount of alkaline matter added. A colour reagent shows when
the solution changes from acidosis to alkaline.