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Final cleaning of tanks prior loading noxious liquid cargo onboard chemical tankers

Method of final cleaning to be used depends on both previous cargo and cargo to be loaded. As a general rule the tanks and piping shall be completely drained of water or residues before loading. The bottom of the tanks may have to be dried up with rags.

Some cargoes are very sensitive to chloride contamination. The tanks to be loaded with these products have to be washed out thoroughly with fresh water. Examples on such products are first of all glycols and alcohols (methanol) but also aromatics and acetates. Vegetable and animal oils, gasoline, heavier oils, caustic soda do not normally require a fresh water rinse of the tanks to be loaded.

chemical tanker navigation at sea
a) Products with good solubility in water: The final cleaning is a direct continuation of the pre-cleaning with water, possibly with hot water for viscous products. If sensitive cargoes are to be loaded any odours that remain must be ventilated and/or steamed away.

b) Volatile products , as mentioned above, do not often require cleaning after discharge.

c) and d) Vegetable oils (drying and non drying) and animal oils are best cleaned by using an alkaline chemical, usually caustic soda, added to the hot washing water. The oil residues will then be converted into soap, which is a water soluble product and which will be rinsed off the bulkheads.

Tank washing process
Final washing in progress

The cleaning chemical is consumed quite rapidly if there are un necessary amounts of cargo left. About 100 kgs of caustic soda are required, counted as a 50 % solution, to saponify 50 kgs of oil. Usually the cleaning chemical is added to the washing water in a 2-3 % concentration of caustic soda (max 5 %. Warning: alkaline washing solutions are dangerous to eyes, use goggles!

IMPORTANT: Zinc silicate tank coatings are adversively affected by alkaline cleaning chemicals. Never use caustic soda or alkaline cleaning agents in zinc silicate coated tanks !

Mineral oils and waxes cannot be saponified. It is possible to remove vegetable and animal oil residues by the use of detergent cleaning chemicals. Detergents reduce the surface tension of the washing water, thus "lifting off" the residues. Cleaning with detergents usually works out more expensive than cleaning with alkaline chemicals but it might be the only solution with zinc silicate coated tanks.

e) Polymerizing products can, after a cold prewash, usually be cleaned off using cold or moderately warm water with a cleaning chemical of a detergent type, emulsifier or with synthetic soap added

f) Heavy oils, lubrication oils, lubrication oil additives, gas oils and similar often account for the most difficult cleaning problems, particularly if demanding products like methanol and aromatics are to be loaded. After the pre-wash: hot washing with cleaning chemicals of a detergent type, solvent cleaner, emulsifier or synthetic soap. Emulsifiers assist in forming minute droplets of the product suspended in the water.

The emulsifiers are usually of a type where one end of its molecules attract water and the other end oil. Soap from an alkaline treatment acts also as an emulsifier. A dosage of 1-2% to the washing water is usually recommended. Certain emulsifiers are so effective that the emulsion will not break up (water and product separate) after a long time, even if heated. If such a washing solution is to be discharged to a slop-receiving facility ashore difficulties may arise. Check with the supplier of the cleaning chemical and the slop-receiver before making your purchase of cleaning chemicals!

"Solvent cleaners" contain water-soluble and hydrocarbon dissolving agents (ketones, aromatics, alcohols), usually in addition to other cleaning effects (alkaline etc). Solvent cleaners often have relatively low flash points: treat them with care, as flammable products.

Detergents contain wetting agents (tensides) which reduce the surface tension of the water, thus "lifting off" impurities from the tank wall.

When several cleaning chemicals are used their sequence of application should be: (water), detergent/alkaline (caustic), synthetic soap, emulsifier, solvent cleaner, solvent.

Leaded gasoline leaves posionous lead compounds on the tank walls which is unacceptable if edible products are to be loaded next.

For edible products the tank is washed with 10 % acetic acid to remove lead remains. This method does not, however, guarantee that the tank will pass a chemist's test and be accepted for edible products. Wine has a particular tendency to absorb lead compounds from the tank walls. Edible products should not be carried until after several other intermediate cargoes.

It is becoming more and more common to apply the cleaning chemical in undiluted form

Related info:
  1. Fixed and portable tank cleaning equipments
    The installation of fixed tank washing machines within a cargo tank allows an inert atmosphere to be maintained during the washing operation, and thus permits cleaning in a closed mode in compliance with port regulations prohibiting release of noxious vapours. Their installation and use also reduces crew exposure to cargo vapours and inert gas.

  2. Tank cleaning and risk with cargo contact
    Different chemicals affect the human body in many different ways. A general information and some practical advice are available in Appendix,7, of "Medical first aid guide for use in accidents involving dangerous goods" published by IMO, WHO and ILO ref (36).

  3. Practical example of solving tank cleaning problems
    Cleaning of tanks is usually the responsibilty of the ship. Tank cleaning and the cleanliness involved have different standards depending upon the previous cargo and the cargo to be loaded. But the matter can be still more complicated, as cleanliness for one and the same product may vary, depending on who the receiver is and for what purpose the cargo is finally intended.

  4. Tank cleaning fatality- case study & lessons learned
    In the trade practice onboard chemical tankers, it is not uncommon that the use of methanol or other chemical/detergents is undertaken to achieve the required standard of cleanliness inside the cargo tank, pipelines, cargo hoses, manifold adaptors/reducers, gauging equipment, etc. Industry publications clearly highlight and caution regarding their use due to their flammability and toxicity hazards.

  5. Pre-cleaning /washing of cargo tanks
    Washing between different grades of cargo is the most common reason for tank cleaning. In most cargo sequences on chemical tankers, this cleaning may consist of no more than a simple hot or cold seawater wash. A simple water wash will disperse many types of chemicals and has been found effective between clean petroleum products such as gas oil and kerosene.

  6. Final cleaning of cargo tanks prior loading
    Method of final cleaning to be used depends on both previous cargo and cargo to be loaded. As a general rule the tanks and piping shall be completely drained of water or residues before loading. The bottom of the tanks may have to be dried up with rags.

  7. Tank cleaning and posoning hazards
    Certain substances affect the tissues locally as an irritant (cashew nut shell oil) or cause grave damage to the eyes, skin or mucous membranes (e g strong acids and caustic). Other substances may be absorbed by contact to the skin without local effects (e g nitrobenzene, aniline).

  8. Testing of tanks and cargoes
    Most common tests and checks for oil and chemical cargoes include testing tank walls for cleanliness. Testing is normally carried out by independent surveyors who, according to local practice or a written agreement in the charter party, are accepted by shipper, receiver and owner.

  9. Practical tank cleaning methods for various noxious liquid cargo
    Tanks that may have contained monomer or drying oils should first be cleaned with sufficient cold water quantities to avoid polymerization of cargo residues. In some cases, it is necessary to employ tank cleaning chemicals, but their use is generally limited as it may be difficult to dispose of slops.

  10. Special tank cleaning method
    If a special method involving cleaning agents is to be used, it may create an additional hazard for the crew. Shipboard procedures should ensure that personnel are familiar with, and protected from, the health hazards 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.

  11. Determining proper tank cleaning by acid wash method
    The acid wash method is used if there is any suspicion that a cargo of aromatics may have been contaminated by a previous oil cargo. The method is also used as a check that a tank is sufficiently cleaned before loading aromatics.

  12. Supervision of all tank cleaning and gas freeing operations
    Tank cleaning is essential on-a chemical tanker, but it must be recognised as a potentially hazardous operation, and rigorous precautions should be observed throughout the process. Together with gas freeing, it is probably the most hazardous operation routinely undertaken on a chemical tanker.

  13. Disposal of tank washings, slops and dirty ballast - safe method
    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 washwater 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.

  14. Cargo tank damage during pigging operations
    Blowing and pigging of pipelines at terminals poses inherent risks for the terminal and a chemical tanker. Frequent damages to tanks have occurred. If there are doubts about the shore operation or signs of problems ashore the OOW must immediately request clarification.

  15. Determining water contamination in chemical cargo
    Presence of free water in non water-soluble products can, very roughly be determined on board by warming a sample of the product in a test tube or in a bottle. Water will then collect at the bottom of the tube and can be seen after some time.

  16. Determining Sulphur contamination (sulphides) in chemical cargo
    Certain products, in particular "virgin naphta feedstock'' (petroleum naphta) are severely contaminated by minor amounts of sulphides (and also lead compounds), which poison catalysts in further processing. Previous heavy oils or dirty harbour ballast water may have left traces of sulphides in the cargo tanks.

  17. Chloride contamination in chemical cargo - how to resolve?
    Certain cargoes are very senstive to chloride contamination, in particular glycols, methanol, ethanol . The tanks should be finally washed with fresh water. However, chlorides (salt) may still be present and a check might be useful. The greatest risk for salt deposits is on horizontal surfaces.

  18. APHA (Hazen) method for determining color of very light chemical products
    A method called APHA (Hazen) is often used for very light products, defined in ASTM D-1209, viz aromatics, ketones. This colour scale is defined with an origin in 100 cc distilled water (value 0) to succesively higher values (max 500) by adding APHA-solution (a platinum-cobolt salt solution).

  19. Loading, discharging & care of Phenol - Safety guideline
    PHENOL is carried at sea in a generally pure state. As a result, it has a high freezing point of approximately 40~ 41deg C. PHENOL is also extremely dangerous when it comes into contact with the eyes or skin and can be fatal.

  20. Hazards of Phenol - safe handling of Phenol on chemical tankers.
    Phenol must be carried at temperatures within charterers instructions, typically between +50 and + 60 degrees C. Heating instructions of the Shipper or Owners must be followed to avoid protests and delays in the port of discharge. Overheating can damage this cargo. A full cargo heating log must be maintained.

  21. Handling benzene & methanol safety precautions
    Benzene is known as a strong carcinogen and known to cause leukaemia. When handling cargoes with more than Benzene concentration of 0.5%, the Master is to ensure that all personnel involved are aware of the long term hazards.

  22. Personal protective equipments for carcinogens & cyanide-like cargoes onboard chemical tankers
    A carcinogen is a substance that may cause cancer by contact or by inhalation. It is therefore essential that the highest safety precautions are taken when handling these cargoes. Access to deck areas must be restricted to duty personnel only. All accommodation doors and ports must be closed and ventilation put on recirculation. Any member of crews involved in cargo operations must wear chemical protective suits and breathing apparatus

  23. Handling ACRYLONITRILE safety precautions
    ACRYLONITRILE are high value and require sophisticated handling for safety, health and loss prevention reasons. They need careful consideration prior loading , tank coating compatibility, cross compatibility with other cargoes carried, environmental controls if required (inerting).

  24. handling ISOCYANATES safety precautions
    Product safety data sheets may be available from various sources. For safety preparation, until the specific product safety data sheet can be obtained, Chemical Data Guide for Bulk Shipment by Water (U.S. DoT), should be used.

  25. Loading, carrying & discharging of Sulphuric acid - regulatory requirements & special handling methods
    IBC code compatibility chart strictly prohibits water in adjacent compartment to Sulphuric acid as you are aware if both come in contact with each other will generate a violent reaction. It is therefore recommended that the during loading of sulphuric acid adjacent ballast tanks to be always stripped dry to the maximum efficiency of the deballasting equipment used.

Other info pages

Draegar Chemical detector tubes use and reading correction guideline
These instruments, often referred to as Draeger tubes, normally function by drawing a sample of the atmosphere to be tested through a proprietary chemical reagent in a glass tube. The detecting reagent becomes progressively discoloured if a contaminant vapour is present in the sample. The length of the discoloration stain gives a measure of the concentration of the chemical vapour which can be read from the graduated scale printed on the tube. Detector tubes give an accurate indication of chemical vapour concentration, whatever the oxygen content of the mixture

Requirements of various grade chemical cargo heating
: The voyage orders will contain heating information, if heating is required. As a rule the final heating instructions are given by the Shipper in writing to the Master / Chief Officer in the port of loading. If those written instructions are not given, the master should request them and issue a Letter of Protest if they are not received at departure. In the latter case the management office should be immediately informed.

Recommended temperature monitoring equipments onboard
:Temperature sensors are fitted so that the temperature of the cargo can be monitored, especially where required by the IBC Code. It is important to know the cargo temperature in order to be able to calculate the weight of cargo on board, and because tanks or their coatings often have a maximum temperature limit. Many cargoes are temperature sensitive, and can be damaged by overheating or if permitted to solidify. Sensors may also be fitted to monitor the temperatures of the structure around the cargo system.

Cargo instruments
:In order to maintain a proper control of the tank atmosphere and to check the effectiveness of gas freeing, especially prior to tank entry, several different gas measuring instruments need to be available for use. Which one to use will depend upon the type of atmosphere being measured.

Liquid level gauges
:The accuracy required of chemical carrier level gauges is high because of the nature and value of the cargo. To limit personnel exposure to chemicals or their vapours while cargo is being handled, or during carriage at sea, the IBC Code specifies three methods of gauging the level of a liquid in a tank - open, restricted or closed

Overflow control
:Certain cargoes require the designated tank to be fitted with a separate high level alarm to give warning before the tank becomes full. The alarm may be activated by either a float operating a switch device, a capacitive pressure transmitter, or an ultrasonic or radioactive source. The activation point is usually pre-set at 95% of tank capacity.

Oxygen analysers
:Oxygen analysers are normally used to determine the oxygen level in the atmosphere of an enclosed space: for instance, to check that a cargo tank can be considered fully inerted, or whether a compartment is safe for entry.

Vapour detection
:Ships carrying toxic or flammable products (or both) should be equipped with at least two instruments that are designed and calibrated for testing the gases of the products carried. If the instruments are not capable of testing for both toxic concentrations and flammable concentrations, then separate sets of instruments should be provided.

Alarm circuit
:An important feature of many modern measurement and control instruments is the ability to signal a particular situation. This can be a main operational alarm that gives an indication of a pre-set situation such as liquid level in a tank, or a malfunction alarm indicating a failure within a sensor's own operating mechanism. The designs and purposes of alarm and shutdown circuits vary widely, and their operating system may be pneumatic, hydraulic, electrical or electronic. Safe operation of plant and systems depends on the correct operation of these circuits and a knowledgeable reaction to them.

Gas freeing
:Gas freeing onboard chemical tankers is required for entry into cargo tanks, for hot works or washing for clean ballast tanks. Gas Freeing is one of the most hazardous operations routinely undertaken onboard a Chemical Tanker and the additional risk created by cargo gases expelled from the tanks, which may be toxic, flammable and corrosive, cannot be over-emphasised.

Cargo tank damage during pigging operations
:Blowing and pigging of pipelines at terminals poses inherent risks for the terminal and a chemical tanker. Frequent damages to tanks have occurred. If there are doubts about the shore operation or signs of problems ashore the OOW must immediately request clarification.

Reference publications

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