CTM 9.10	Chemical Tanker Manual CTM Carriage and Handling of Special Cargoes	Doc No.: CTM 9.10 Revision: 01 Date: 15 Oct 2024 Issued by: DPA Approved by: MD

1.APPLICATION

This document applies to all Chemical Tankers managed by Company.

2.PURPOSE

The purpose of this document is to specify requirements and procedures for the safe and efficient carriage and handling of special cargoes.

3.RESPONSIBILITIES

Chief Officer is responsible for the safe and efficient handling of special cargoes, unless otherwise decided and authorised by Master.

4.CORROSIVE CHEMICALS

For description on hazards of corrosive chemicals see CTM 9.2 Appendix 1 Hazards of Chemical Cargoes.

4.1 General precautions when handling corrosive chemicals

Protective Equipment

See FOM 10.10 Personal safety.

Further Reference - CHRIS code/NFPA health hazard rating and MSDS.

Exposure to personnel and first aid

• First aid kits: Before start of any cargo work, prepare first aid kits and medicines at hand.
• Storage position: Mark and make it known to personnel involved in cargo operations.
• In case of any exposure with injury to personnel: Call for professional medical assistance immediately.
• Provide First aid: Prior to arrival of doctor.
• If the patient gets burns, first remove the acid. Early removal will enable subsequent easier treatment.

Precautions before transfer

• Stainless Steel Acid Spray Shields: Have sufficient to cover flanges on manifold & hose connections. (Ref IBC code 15.11.4 and BCH code 4.8.4).
• Other work: Prohibit work other than cargo work.
• Acid resistant hoses: Have sufficient for the cargo transfer and in good condition.
• Pressure test: The loading lines prior loading.
• Soap test: Once shore connections are made, soap test the entire line for leak detection.
• Gaskets: Check the condition of gasket of flange connection and tools. Gasket must be Teflon and tools must be of non-spark type.

Precautions during transfer

• Start at a slow rate. Check status of ship's lines, cargo hoses and pumps.
• Increase gradually - the rate and pressure as planned.
• Monitor Closely - the loading rate and maintain as agreed.
• When changing loading tank, be careful with the valve handling:
  1. Open next set of tanks prior to closing the valves of the currently running tanks.
  2. Handle valves slowly and smoothly to prevent pressure surge in the cargo line.
  3. If any leaks are identified, suspend loading and immediately rectify the same.
• High specific gravity: Due to high specific gravity, keep careful check on backpressure in the line.
• On completion of discharge: Do not open any tank opening to prevent oxidation in damp air.

Precautions after transfer

• Remove remaining liquid in cargo lines.
• Spilling: Exercise care to prevent any liquid from spilling.



Coution:

• Whatever method used, it must be thorough enough to ensure that there is no liquid left in the line prior disconnecting.


• When disconnecting cargo hoses (or loading arms):
  • Open the drain valve slowly to release the pressure in the line.
  • Drain the remaining liquid, if any, into the drip pan.
  • Open the flange connection at the manifold.
• When loosening the flange bolts: Start from the lower part to allow flow of remaining cargo, if any, downward.
• After completion of cargo work, close all the valves prior to disconnection of hoses.

Precautions for opening manhole

• Prepare and wear the necessary personal protective equipment (PPE).
• Place a bucket full of fresh water or have running fresh water from the ship's line beside manhole hatch.
• Wash and clean protective equipment soon after completion of taking ullages or taking sample.
• When opening manhole hatch-cover:
  1. Loosen bolts and nuts slowly to release the pressure in the tanks slowly.
  2. Watch out for vapour release or splash of the acid.
• To avoid inhaling vapour and mist: Stand near the hatch at 90° to the relative position of wind direction.

Jettisoning of cargo in emergency

See CTM 9.9 for general instructions. For corrosive cargoes, the following particulars apply:

• Discharge through underwater overboard line is not recommended.
• Choose safe waters to discharge and proceed with wind direction from astern.
• Connect Cargo hose for discharging to the leeward manifold.
• Set the cargo hoses overboard:
  • Apart from the hull as far as possible.
  • Put into the sea as deep as possible.
• Wear appropriate PPE as per FOM 10.10- Personal Safety.
• If possible, do not use the sea suction line on discharge side.
• Close all the openings of the deckhouse.

Tank cleaning

Also see CTM 9.7 Tank Cleaning. Specifically, for acids:

• Commence washing with fresh water as soon as possible after discharge.
• Keep tank sealed if washing cannot be commenced soon after discharge. This is to prevent oxidation by damp air.



Note:

• Oxidation leads to tank discoloration in the case of acids. The tank changes colour to brown, green and sometimes black.




Note:

• Acids are more corrosive at lower concentrations, e.g. Sulphuric acid is most corrosive between 20-80% concentration


• Before commencing fresh water Butterworth:
  • Start the cargo pump and pump out residues left in the cargo tank bell mouth.
  • Introduce large quantities of fresh water into the tanks. This is to reduce the concentration of acid in the tank rapidly to below the required concentration.
• Thereafter commence washing through Butterworth machines.
• Operate cargo pump continuously to prevent any build-up of washings in the tank.
• Do not collect the cleaning water in any other tank. This will damage the tank structure.
• Discharge the washings using cargo hoses on the leeward side as deep as possible into the sea.
• Continue washing until PH value is 7.
• If the PH value of 7 is not obtained after washing for 30 minutes in 2 steps (3m/15min, 7m/15min), stop the wash and gas-free the tank.
• Once the tank is gas-free, the crew must wear relevant PPE and hand wash the tank with fresh water, especially:
  • Under the heating coil,
  • Behind the pump stack, and
  • On the U-clamps securing the coils and other blind sectors.
• On completion of above:
  • Check the PH value at the pump stacks and
  • Keep washing until PH 7 is achieved.
• On completion of washing, mop/dry and gas-free the tank to prevent oxidation.
• Keep the tank dry for 1 – 2 days.
• On completion of tank cleaning and gas freeing, make tank entry to check closely for corrosion in the following areas in the tank:
  • Tank top plate and suction well,
  • Tank walls at lower section,
  • Welding seams,
  • Cargo pump, including impeller, mouth ring, casing, pump supports and bolts/nuts,
  • Cargo line, especially at welding seams,
  • Heating coils, especially welding seams, bolts/nuts of pipe supports,
  • Level gauge, including guide pipe, supports of guide pipe and float,
  • Ladder and its accessories at lower section,
  • Valves and drainpipes including disc and seat, spindle and drain cocks/valves and plug,
  • Cargo lines, especially welding seams and sagged parts which have pockets to retain cargo.

4.2 Sulphuric Acid - General

Refer to 4.1 General precautions when handling Corrosive Chemicals.

• Prepare seawater or fresh water hoses at the site of the working area to be able to use large amounts of water in anticipation of leakage of the acid, accidental exposure to crew, etc.

Precautions for Stowage Planning

• Do not load the following in adjacent tanks:
  • Reacting substances
  • Heated cargoes
  • Ballast water



Note:

• Sulphuric acid is hygroscopic and will accelerate acid attack in ullage space. To protect Stainless Steel in vapour/ullage space, cargo tanks to be padded with Nitrogen in case ship has working nitrogen generator.(this is to protect owners interest/optional as IBC does not require tank environmental control). In case ship does not have nitrogen generator, check Stainless steel manual from makers or check with makers and follow their recommendation.


• After loading, drain all cargo lines and blow back to tanks.

As the specific gravity of acids is high, decide loading quantity considering the "Designed S.G." of the tank construction.

Preparation of Tank for Loading Sulphuric Acid

• Completely dry-up the tanks, cargo lines, and vent lines.



Note:

• Dry and empty adjacent ballast tanks as well.


• Remove oily substances, dried residue of previous cargoes, and traces of detergent.

Cargoes That Require Special Care When the Next Cargo Is Sulphuric Acid

• Most cargoes are suitable as the next cargo for Sulphuric acid.
• In case of loading reactive cargoes such as alkali (amines and caustics), remove acidity by residue of sulphuric acid completely by cleaning, and checking the PH value of tank bulkheads, bottom, and lines with litmus paper.

Cargoes That Require Special Care When the Previous Cargo Is Acid

• Solidifying cargo such as Wax
• Polymerizing cargo
• Amines
• Mineral Oils (Fuel Oil, Lubricating Oil, Naptha)
• Creosote, Cresol, Resin Oil
• Strongly remaining Hydrocarbons such as Phthalate
• Vegetable oil and Animal oil
• Cargoes containing water and remaining dry residue such as Lignin Pitch, Caustic Soda

Tank Cleaning

See 4.1 General precautions when handling Corrosive Chemicals – Tank Cleaning.

• After discharge, preferably use Fresh water to clean the tanks as soon as possible.
• If Fresh water is not available, add large amounts of seawater to the tank.



Note:

• In addition to using all available tank-cleaning machines put additional water into the tank, using ballast or other available pump, through the drop line.


• Ensure that the tank and its associated line system are cleaned until all deposits are washed out and a neutral PH value is obtained.

4.3 Phosphoric Acid

Refer to 4.1 General precautions when handling Corrosive Chemicals.

Characteristics

• Wet PAC – dark brown in color.
• Ortho Phosphoric - colorless crystal at room temperature.
• Melts at 21°C (Pure).
• In its liquid form, it is a clear syrup.
• Is soluble in both water and alcohol.
• May cause corrosion on stainless steels.

General Precautions

• Master/Chief Officer shall:
  • Before loading, check the quality of cargo by asking the operator or surveyor.
  • Ensure composition is within stated limits or does not exceed the following maximum ranges:
    • Concentration of P205: 48 – 54%
    • Concentration of CO4: max 4%
    • Concentration of chlorides: max 200 PPM
    • Temperature: max 45°C
  
  

  Coution:

  • Any value in excess of any 2 items of above will damage and discolour the tank.
    Do not accept such cargo, contact Marine Superintendent/ Marine Department for advice.
  
  
  • If it is expected that the cargo contains sediments, ensure sufficient portable acid-resistant equipment for recirculation of cargo.
  
  

  Coution:

  • Expect high wear and tear on pumps cargo seals from acid containing sediments.
  
  
  • Ensure cargo pump seal (cargo seal & oil seal) integrity is examined prior to loading.
  
  

  Note:

  • If the vessel has diffusers then all nominated cargo tanks to be fitted with the diffusers prior loading the cargo.
  
  
  • Re-circulate the cargo daily to minimize the sediments/gypsum settling at the bottom of the tank.
  • During final discharge when the liquid level is about 1m, re-circulate the cargo to reduce the sediments and maximize cargo output.
  • Rinse and flush all cargo lines with fresh water, if not gypsum with seawater will attack the weld seams and will lead to pinholes and pitting.
  • Cofferdams must be purged and flushed with fresh water & test the cofferdam as pinholes and pitting may be expected on the purge pipe (for both H3PO4 & H2SO4).
  • Check the passivity of stainless tanks after carriage of acids (for both H3PO4 & H2SO4).
  • Passivation must be carried out to regain the chromium oxide layer, if cargo tanks are subjected to three consecutive acids (for both H3PO4 & H2SO4). This should be on charterers' account/this is to protect owners' interest/optional.
  • Fit hydrogen gas detectors in rubber-coated tanks as H3PO4 gives out hydrogen gas when it reacts with mild steel (breakdown of rubber coating).
  • Prior to loading, test rubber-coated tanks for coating damage with the detector & repair accordingly.

Grades of Phosphoric Acid and Associated Precautions

Phosphoric acids are shipped as different grades which may vary in purity and acid concentration (e.g., food grade, wet processed fertilizer grade, commercial, etc). Some examples of types of grades of Phosphoric acid are given below:

4.3.1 Pure Phosphoric Acid (80% solution):

• Used as additives in food and beverages.
• Very high degree of tank cleanliness is necessary. Check with the ship operator if a wall wash is required.
• Freezes at 5°C.
  • Arrange for heating in cold climates.
  
  

  Coution:

  • Do not use Steam for heating, as maximum allowable coil temperature is 90°C.
  
  
  • Carry out heating with adjacent cargoes or by use of water or thermal oil.

4.3.2 Wet Process Phosphoric Acid:

• Almost all contain solid particles that may form adherent deposits.
• The steel surface of the tank top may be attacked during the voyage. Prepare arrangement to circulate the liquid above the tank top.
• In some cases, the cargo may be loaded at temperatures greater than ambient. This can have an adverse effect on the stainless steel.



Coution:

• Master shall consult Marine Superintendent/ Marine Department before loading Phosphoric Acid that is over 40°C.



Note:

• If the temperature of the acid is exceeding 50oC the cargo will normally not be loaded.


• The solids (impurities) in the WPA will quickly settle out and build up a thick heavy sediment layer on the tank top.
• This sediment layer, if left undisturbed, could block the pump impeller and make pumping impossible.
• To prevent pump blockage, apply 10 blows to the pump stack with compressed air at least once a day.
• Run the pump slowly, a few minutes to ensure that the impeller is operating freely.

4.3.3 Super Phosphoric Acid (SPA):

• Excessive heat rapidly degrades the SPA.
• At temperatures below 60°C, it becomes very viscous and un-pumpable.
  • Heat and keep the SPA at a temperature of 65°C.
  • Maximum temperature: 82°C.
  • Minimum temperature: 60°C.
  • Ensure maximum allowable temperature on the heat media is 90°C.

Acid Leak Detection

Refer to the IBC Code 15.11.7, BCH Code 4.8.7: "Provision shall be made for suitable apparatus to detect leakage of cargo into adjacent spaces."

Cargo Line and Hose Precautions

• Because of the high specific gravity of Phosphoric acids, very high pump pressure may be experienced.
• In such cases, take care not to quickly open or close valves in the pump system as this causes pressure surges that may rupture lines or hoses.

Sediments

• Rig portable equipment (acid-resistant hoses and tank cleaning machines), from pump stack to available tank openings.
• Discharge the small tanks first.
• Flush sediments out of the first empty tank by using "good acid" from another tank.



Note:

• It may be necessary to position the machines (vertically & horizontally) to break down lumps of sediment.


• When the first tank has become "sediment-free," refill the same tank with "good acid." Use this when flushing the sediment from the last remaining tank.

Tank Cleaning

See 4.1 General precautions when handling Corrosive Chemicals – Tank Cleaning.

• After discharge, preferably use Fresh water to clean the tanks as soon as possible.
• If Fresh water is not available, add large amounts of seawater to the tank.



Note:

• In addition to using all available tank-cleaning machines put additional water into the tank, using ballast or other available pump, through the drop line.


• Ensure that the tank and its associated line system are cleaned until all deposits are washed out and a neutral PH value is obtained.
• After cleaning, remove any remaining chlorides from the tanks as soon as possible by steaming and mopping the condensed water.

5 ACETONE CYANOHYDRIN (ACY)

5.1 Description

• Comprises of Acetone and Hydrogen Cyanide.
• Highly unstable.
• To make them stable, these are placed in Sulphuric acid of 100% concentration.
• High exposure leads to instant death.
• The acid would penetrate the skin and allow systemic absorption of the Acetone and Hydrogen Cyanide.
• This would lead to inability within the body to absorb oxygen molecules.
• Though able to breathe, a person would be gasping for breath owing to the inability of the body to absorb the oxygen from the air.

5.2 Precautions and First Aid General Precautions

• Exercise extreme caution whilst:
  • Connecting and disconnecting hoses,
  • Opening Butterworth ports, and
  • During tank cleaning operations.
• As a policy during all these operations, all personnel on deck shall wear SCBA.
• ACY decomposes with the addition of water and gives off Hydrogen Cyanide gas.
• A small amount of water added to a comparatively large volume of ACY results in a violent reaction.
• ACY is an IMO pollution CAT A cargo which requires a pre-wash.
• Carry out pre-wash with a large amount of fresh water.
• There is no known risk if plenty of fresh water is added to a comparatively small amount of cargo.
• In case of contact with the body, wash the exposed part with copious amounts of fresh water.
• Administer anti-dotes as per below.

Administration of Anti-Dotes for Cyanide Poisoning

• Exposure can be fatal. Even a drop of the liquid on the skin would cause penetration through the skin.



Warning:

• Systemic absorption of cyanide would lead to rapid death within 6 minutes Quick diagnosis and very prompt use of anti-dotes is paramount.


• Break an ampoule of Amyl Nitrite, one at a time, in a handkerchief.
• Hold it in front of the patient's mouth for 15 seconds – followed by a rest of 15 seconds.
• Then re-apply until Sodium Nitrite can be administered. This interrupted schedule is important because continuous use of Amyl Nitrite may prevent adequate oxygenation.
• Discontinue administration of Amyl Nitrite and inject intravenously:
  • 300mg (10ml of a 3% solution) of Sodium Nitrite at the rate of 2.5 to 5.0 ml per minute.
• The recommended dose for children is 6 to 8 ml per square meter (approximately 0.2 ml/kg of body weight), but should not exceed 10 ml.
• Immediately thereafter, inject 12.5g (50 ml of a 25% solution) of Sodium Thiosulphate for adults.
• The dosage for children is 7 g per square meter surface area, but the dosage should not exceed 10 ml. The same needle and vein may be used.
• If the poison was taken by mouth, perform gastric lavage as soon as possible, but this should not delay the treatment outlined above. Lavage may be done concurrently by a third person, if available.

Post Administration

• Watch the patient for at least 24 to 48 hours.
• If signs of poisoning re-appear, repeat injection of both Sodium Nitrite and Sodium Thiosulphate, but each in half the original dose.
• Even if the patient appears perfectly well, the medication may be given for prophylactic purposes two hours after the first injections.

If Respiration Has Ceased But the Pulse is Palpable

• Apply artificial respiration at once. The purpose is not to revive, per se, but to keep the heart beating.
• Lay the gauze, sponge, or handkerchief containing the Amyl Nitrite over the patient's nose. This may hasten the resumption of respiratory movements.
• When signs of breathing appear, inject the above solutions promptly.

6 ACRYLATE MONOMERS

6.1 Examples

• Butyl Acrylate
• Ethyl Acrylate
• Methyl Methacrylate
• Butyl Methacrylate

6.2 Temperature Monitoring and Jettison Procedure for Acrylate Monomers

Emergency actions are triggered by:

• Specific temperatures or
• Speed of temperature rise at any temperature.

In general, follow actions A through D as outlined below.

A. If, on any of the temperature indicators, the cargo temperature has increased by:

• 3°C or more in a period of 4 hours, or
• 10°C or more in a period of 24 hours, or
• Has reached 3°C higher than the cargo temperature at loading and is over 40°C, the following actions are required:

1. Check temperature every 30 minutes.
2. Plot on graph paper.
3. Investigate (by physically checking) and remove the source of heat. (Non-compliant adjacent cargo, hot water system problem, pump circulation).
4. If source of heat is found and removed, monitor temperature at 30-minute intervals for at least 4 hours. Temperature should stabilize or drop.
5. If no source of heat can be found and removed, call Marine Department/Shippers.
6. If adjacent tanks are empty, fill these with water.
7. If adjacent tanks are full, turn off heat to these tanks.
8. Line up for circulation either through existing drop line or rig portable hose.
9. Marine Department will contact Shippers’ Emergency Response contact.
10. Send cargo and adjacent tank temperature logs for the last 24 hours to Marine Department and Shippers’ ERT.

If the cargo temperature:

• Increases by 1°C or more in a period of 30 minutes without identifiable cause, or
• Reaches 45°C, the following actions are required:

1. Begin circulation of cargo and blow air into the cargo through the drop line.
2. If possible, sample to observe for haze as an indication of polymer presence.
3. Continue temperature monitoring. If the cargo temperature:
• Is still increasing by 1°C or more in a period of 30 minutes without identifiable cause, or
• Reaches 50°C, take the following actions:
1. Prepare to pump cargo overboard.
2. Add cold fresh water to tank as much as void space and fresh water availability permits. Continue circulation. Continue adding fresh water until tank is full.
3. Monitor temperature closely.
4. Vent pressure and unbolt/unlatch manways to tank; but do not remove.
5. Prepare fire hose for vapor knockdown at manways.

B. If the cargo temperature:

• Continues to rise by ≥2 °C since the last reading (30 minutes) without identifiable cause, or
• Reaches 55°C, take the following actions:

1. Begin pumping cargo overboard.
2. Continue adding fresh/salt water while cargo is being discharged.
3. Begin preparation of back-up pump-to-pump cargo from top of tank in case primary pump plugs with polymer.
4. Point ship up wind and keep people up wind as much as possible until tank is empty.
5. Monitor tank level, use back up pump if primary pump plugs.
6. When tank is empty, start cleaning with cold water and continue cleaning until tank is clean.

6.3 Decision Help Table

Load temp =

Load temp plus 3°C = Load temp + 3°C = Put this result in Box below

Load Temp	Load Temp + 3°C	Put this Result in Box Below	Rate of Temperature Rise	Temperature Action(s) to	Temperature Action(s) to
3°C or more in 4 hours	3°C	A	10°C or more in 24 hours	A	A
More than 25°C and	25°C	A	40°C or more	A
1°C or more in 30 minutes	1°C	A & B	45°C or more	A & B
Continuing 1°C or more in 30 minutes	1°C	A, B & C	50°C or more	A, B & C
2°C or more in 30 minutes	2°C	A, B, C & D	55°C or more	A, B, C & D

6.4 Preparation for Loading

• Clean tank to water white condition, including vapor lines, all bleed valves.
• Work all ball valves in lines and clean bleeds on pressure gauges.
• Do not purge tank or lines with nitrogen.



Note:

• The inhibitor stabilizing the cargo requires oxygen to keep the cargo stable.
  Confirm this from the shipper’s prior loading.


• Check that the P/V valve (Pressure/Vacuum) functions normally.
• Blind off heating coils/media.
• Set high ship tank(s) temperature alarm(s) at 38°C. Test all instruments connected to the tank.
• Adjacent tanks or ballast space must not contain cargo or ballast with a temperature greater than 38°C in transit.
• Ensure that all personnel handling this product have been trained and informed about specific hazards.
• Product information and procedures must be on board vessel before loading.

6.5 During Loading

• Confirm that the cargo to be loaded has a temperature not greater than 38°C. Normal temperature range is ambient to 38°C.
• Ensure that the Shipper’s MSDS has been received on board.
• Inhibitor certificate received on board containing required information.
• Dock hose and vapor line connected to correct manifold.
• Check and log the cargo temperature.
• Do not use nitrogen to clear lines after loading. Install ‘Do Not Use Nitrogen’ tags.

6.6 In Transit

• Check and log the cargo, adjacent tanks, and seawater temperatures.
• Keep cargo temperature below 38°C during the voyage.
• Keep deck water running to keep deck cool.
• Drain P/V vent stacks twice a day.



Note:

• This is to be done to ensure that there is no condensate in the stacks, which may polymerize. Please note there is no inhibitor in the condensate and hence it can polymerize.


• Wrap the P/V vent stacks with gunny bags and keep same wet to keep the temperature of these pipes ambient.
• After the first 24 hours, check and log the following temperatures every 8 hours:
  • Cargo of Monomer,
  • Tempered water,
  • Adjacent tanks,
  • Sea water

6.7 Discharge Procedure

• Confirm that tank temperature is below 38°C.
• Ensure the shore hose and vapor recovery line are clean, dry, and connected to the correct manifold.
• Do not add nitrogen to the tank since the inhibitor stabilizing the cargo is oxygen dependent.
• Gauging and sampling will be done by the receiver’s surveyor.
• Preferably discharge this cargo at a temperature below 38°C.
• Check and log the temperature during discharge.

7. SOLIDIFYING / HIGH VISCOSITY CARGOES (CDI 5.5.8)

7.1 General Information

• Solidifying cargoes commonly carried are of the following types:
  • Non-dry type vegetable oils and animal fat
  • Chemical cargoes (Annexe II) which require heating.
  • Cargoes liable to polymerize under the influence of heat and/or light.



Coution:

• Serious problems can occur due to minor faults of handling and maintenance.


• Take necessary precautions for cargo operations involving solidifying cargoes, especially those included in Group 2 in the table below.



Coution:

• Cargoes in Group 2 will swiftly be solidified and thereafter a long time will be required for melting as compared to an animal and a vegetable oil.


• If the cargo operation is suspended and considering the ambient temperature, all cargo lines must be drained & blown back inside the tanks to avoid clogging of cargo lines.
• Re-circulate crude vegetable oil products regularly to minimize sediment settling down at the bottom.
• During sailing, kick start the cargo pump with the discharge valve shut to ensure the impeller does not freeze (especially when the vessel is on a long voyage).

Group	Name of Cargoes
Group 1	Coconut oil Hydrogenated corn oil Hydrogenated rapeseed oil Palm oil Kapok oil Peanut butter Hog grease (lard) Tallow

Group

Name of Cargoes

Group 2

Acetic acid Benzene Tert-butanol Cresol Cyclohexane Para-dichlorobenzene Dichlorobenzene Dimethyl aniline (DMA) Ethylenediamide (EDA) Fatty alcohol Formic acid Hexamethylene diamine (HMDA) Naphthalene Nitrobenzene O-nitrochlorobenzene N-pentane Phenol Polypropylene glycol Polyethylene polyamine Poly isobutylene (PIB) Polysiloxane Potassium hydroxide solution Toluene Diisocyanate (TDI) Undecyl alcohol Para-xylene

Group	Name of Cargoes
Group 3	Acetone cyanohydrin (ACH) Ethyl acrylate Ethyl methacrylate Alpha-methylstyrene 1,3-pentadiene Styrene monomer (sm) Vinyl acetate monomer (VAM) Methyl acrylate (ma) Methyl methacrylate (MMA) Other acrylates

7.2 Preparation of Personnel Protection

• In case of handling solidifying cargoes of categories Group 2 and 3:
  • Use suitable personnel protection equipment.
• If nitrogen gas is used in cargo operation, in addition to the above:
  • Oxygen resuscitator
  • Self-contained breathing apparatus
  • Air-line type gas-tight suit, if available

7.3 Line Blowing

• Vessel and terminal representatives shall carry out a meeting before line blowing.
• At the pre-meeting, the following shall be discussed and agreed:
  • Method of blowing
  • Media (air, steam, or nitrogen)
  • Arrangement for line-up
  • Number of times of blowing
  • Shore (or barge) facilities and method for blowing from shore
  • Whether blowing is performed from shore (or barge)

7.4 Checks Before Loading

• Check cargo-heating system:
  • Drain water from heating pipeline and steam pipeline by air blowing.
  • Start steam slowly and check for leakage in pipelines in the tank and on deck.
  • Ensure steam traps are in good condition.
  • Inspect heating coils along with the surveyor.
• If the vessel carries heat-sensitive cargoes, which are prone to polymerize, then blank the steam inlet line.
• Perform leak check of valves.

7.5 Checks of Submerged Pump

• Ensure no remains of previous cargo in pump cofferdam.
• Carry out cofferdam purging to confirm.
• Confirm cargo line drain is free prior to loading.
  • There are pockets that are difficult to keep clean and from stagnation.
• Check the location on the pipelines that are prone to stagnation before loading.

7.6 Checks After Loading

• Request air or nitrogen for blowing from shore for removing remaining cargo in pipelines.
• Take into consideration the difference between:
  • Loadable tank volume to go and
  • Estimated cargo quantity to be blown.
• After the shore hose is disconnected:
  • Blow the remaining cargo in each pipeline of each cargo tank.
• After loading operation, use hot water or steam to melt out solidified cargo in the pipeline including drain pipes.
• On vessels equipped with submerged pumping systems:
  • Leave the filling and delivery valves open for a few days.
  • This to prevent cargo residues remaining in the pipeline from solidifying.

7.7 Checks During Voyage

• Maintain the temperature of cargo as per its heating instruction.
• Check the condition of tank bottom by a sounding tape or rod at regular intervals during the voyage.



Coution:

• If nitrogen padding was carried out in the tank or toxic/hazardous atmosphere is suspected in the tank then such check is strictly prohibited.


• Check if cargo is solidified in the pipeline of pump stack or at the position of manifold.
• For vessels equipped with deck heater systems:
  • Follow maker’s instructions to check for the condition of pump pipeline, heating unit, and heat exchanger, etc.
• Before starting to heat:
  • Take the drain water in heating coil from the return line.
  • Check whether there is odor or pollutant.
  • Keep the main return valve closed during the above.
• During normal heating, check coil drains regularly for leakages.
• Carry out cargo pump cofferdam purging according to the maker's instruction manual.
• In case closed cargo circulation is being carried out:
  • Ensure that the isolation valve and the manifold valves are shut.
• Always air-blow the pipelines used for circulation of cargo after completion of circulation.
  • If the atmosphere of the tank is under nitrogen gas, do not blow into such tanks.
• To prevent the polymerizing of cargo from solar heat:
  • Consider cooling the deck within the cargo area by sprinkling water.
  • Vent pipeline can be covered by wet lagging or with a wet waste rag.

7.8 Checks Before Unloading

• Prior to commencement of discharge of solidifying/high viscosity substances such as lubricating oil additive, lignin pitch, tall oil, caustic soda, and molasses etc.:
  • Circulate such cargo through the drop line or by-pass line without opening the manifold valve and isolation valve.
• Start discharging operation only after confirming that cargo is not solidified.
• Start the cargo pumps slowly and carefully after opening the valves.
• Monitor pressure at the manifold closely.

7.9 Checks After Unloading

• Hammer test the cargo line to check if any cargo is trapped in the line.
  • The hammer used for testing must be of non-spark type.
• Check valve status – Check each valve in the pipeline that had been used for cargo operation to be ascertained for correct operation by fully opening and fully closing.
• The above check is required to ensure no cargo residue remains in the pipeline underneath the valve body.
• Leak check for mechanical seal of the cargo pump shall be carried out.
• The following precautions are to be taken if parcels of solidifying cargo are unloaded at different ports:
  • Line-blowing shall be carried out after every partial discharge.
  • When a solidifying cargo is discharged or drained through the manifold, each drain line/common line, each spool piece shall be blown or cleaned up, and jumping hoses shall be cleaned up and drained out.
• When a polymerized cargo is discharged through the common line, the above two items shall be carried out as the first step, and the spool piece attached to the common line removed and washed using ambient water and dried.

7.10 Conclusion

• The critical points for safe handling of solidifying cargoes are as follows:
  • Inspection of cargo heating system to be performed prior to loading.
  • Leak-check for valves related to cargo work to be carried out prior to loading.
  • Line-blowing shall take place for a sufficiently long time, and checks be made to ensure that lines are free of cargo after loading.
  • Cargo heating shall take place as per heating instructions provided.
  • Cargo and vent lines shall be confirmed to be free from any cargo residue during the voyage and before entering a discharging port (Solidifying of cargo in the vent line).
  • Clearing of solidified cargo in the pipelines shall be carried out by heating the pipeline's surface safely.
  • Safety meetings shall be held prior to loading to ensure that the crew is familiar with the hazards of the cargo.
  • When carrying cargoes that freeze at ambient temperatures, the vent lines and P/V valves must be regularly checked to ensure that vapours do not freeze or crystallize in the lines or valves and block them. The design of the cargo tank and equipment has temperature limitations, and care must be taken not to exceed these temperature limits. Excessive heat may reduce the strength of the steel and increase the risk of cracks or damage to the coating.
  • When carrying heated cargo, special consideration shall be given to the possible effects of heat transfer to unheated cargoes in adjacent tanks, particularly if cargoes are self-reactive or have a high vapour pressure.

8. TOLUENE DIISOCYANATE (TDI)

8.1 Operational Procedures for Isocyanates

• The isocyanate must not come in contact with humidity; dew point must be less than 40°C in the tank before loading commences and during transport. Refer to IBC code 9.1.2.3, 15.16.2.
• All parts of the cargo system must be purged with N2 to the required dew point, including vapor/return lines. Work all ball valves and drain plugs during purging. Remove plug in ball valve housings and verify they are dry.
• Heating coils shall be blown dry with N2 and blanked off.
• Pump cofferdam shall be filled with Dioctylphthalate (DOP) as this will not react with the Isocyanate if leakage occurs. If DOP is not available, purge the pump cofferdam with N2 and maintain a low flow through the cofferdam during loading, transport, and discharging.

8.2 Emergency Procedures

• Fire: Use dry powder, alcohol-resistant foam, carbon dioxide, or halons. Firefighters must wear breathing apparatus.
• Liquid in eyes: Flush the eye with plenty of clean sea or fresh water for at least 15 minutes. Call a doctor and take the person to the hospital.
• Liquid on skin: Remove contaminated clothing and wash affected areas for at least 15 minutes with soap and water. Take to hospital.
• Inhalation: Remove the victim to fresh air and rest. If breathing is irregular or difficult, give artificial respiration. Immediately call for professional medical attention.
• Spillage: Soak up with sand or other inert material. Render the remainder harmless with dilute spirits of ammonia. Wear a breathing apparatus.

9. LATEX (SYNTHETIC)

9.1 General Information

• Product: Latex liquid synthetic
• Shipping Name: Latex
• Product Description: Milky white liquid with a slightly aromatic odor. There are several grades; check the specification from relevant shippers before shipment.
• Trade name: Latex liquid, synthetic, styronal
• Main Hazards: None
• MARPOL Category: APP.3
• USCG Comp Number: 43
• Not compatible with: Benzene Sulfonyl Chloride (O)

9.2 Operational Procedure

• Prior to loading: After the tank is accepted for loading, steam the tank through the Butterworth hatch and manifold line for at least 15 minutes.
• After loading: Immediately after loading, fill the manifold line with fresh water to avoid drying of Latex in the line. Ensure all tank valves are kept closed during passage. Steam the tanks through the vapor return line and vapor lock at least twice a day for 15 minutes to keep the bulkhead moistened and prevent drying of latex.
• During discharge: Steam the tank through the Butterworth hatch for at least 15 minutes every hour. Ensure the Butterworth pockets are covered with burlap.
• After discharge: Prewash the tank immediately to shore after discharge is completed and the empty tank certificate is issued. If for some reason tank cleaning is delayed, steam the tanks to prevent the latex from drying.

9.3 Cleaning of Latex

Procedure 1

• Cold seawater wash for 2 hours.
• Rinse with fresh water and pump out remaining water in the tank to ensure 100% pure PCE.
• Circulate PCE (3 to 4 x 200-liter drums) for 2 hours using extra portable tank cleaning machines on the Butterworth hatch in two steps (Ensure all safety precautions are taken, cover the Butterworth hatch to avoid the escape of PCE).
• Transfer the PCE solution to another tank.
• Cold seawater wash for 2 hours.
• Fresh water rinse.
• Depending on the next cargo, follow the tank cleaning guidelines as required.
• Remark: Inspect the cargo tank after gas-freeing. If small patches of latex are found near the tank hatch or behind the discharge pipe, use toluene to wipe it out.
• Example: For 2 small tanks loaded with Latex, 5 x 200-liter drums of PCE can be used. 4 drums can be used in the first tank and the remaining 200 liters can be added when transferred to the second tank.

Procedure 2: Cleaning Latex with TPU Cleaning Mix

• TPU Cleaning mix is the combination of "Green strip" and "WS-3 Latex Skin Cutter." Use 100 liters of WS-3 per 1000 liters of water, and 4% (by weight) of Green strip, which is 44 kg in 1100 liters of the water/WS-3 mix. The pH of the solution should be 12.5, and no lower than 10.
• Pre-clean the tank with fresh water for 30-60 minutes. Never use seawater.
• Make a solution of freshwater and cleaning mix as described above.
• The solution must be sufficient to cover the heating coils, so if one set is not enough, use two sets. Heat the solution to above 90°C.
• Re-circulate the wash for about 2 hours. If necessary, reheat the solution.
• Flush with cold freshwater until all cleaning material is gone.
• The solution can be used up to 50 times, so if possible, store it for the next cleaning of latex.

10. ACRYLONITRILE

10.1 Characteristics

• Acrylonitrile is an unstable product when not inhibited.
• Acrylonitrile is regulated for bulk transportation by the IMO, BCH, and IBC codes. Following is a summary of the codes' minimum requirements:
• UN number: 1093
• Pollution category: Y
• Hazards: Safety and pollution hazard
• Ship type: 2
• Tank type: Integral gravity tank
• Tank vents: Controlled venting
• Tank Environment: No requirements
• Electrical equipment: Special requirements
• Gauging: Closed
• Vapour Detection: Flammable and toxic vapours
• Fire Protection: Alcohol resistant foam
• Material of construction: Aluminium, magnesium, zinc, galvanized steel, and lithium shall not come in contact with Acrylonitrile. Materials normally used in electrical apparatus such as copper, aluminium, and insulation should, as far as practicable, be protected to prevent contact with the vapour of Acrylonitrile.

10.2 Special Requirements

10.2.1 General

• See IBC Code, Chapter 15, 15.12, 15.13, 15.17, 15.19 and the BCH Code, Chapter IV, 4.9, 4.10, 4.12.3, 4.13.1, 4.14, 4.17.

10.2.2 Respiratory and Eye Protection

• Individual units are required for emergency escape purposes.

10.2.3 Special Arrangements, Safety Alert, and Chemical Incompatibility

• Acrylonitrile/caustic soda solution: Recent laboratory tests indicate a potentially hazardous reaction between acrylonitrile (group 15) and caustic soda solution (group 5). This combination is considered compatible for adjacent stowage by current regulations (46 CFR part 160). However, new data shows that a delayed reaction may occur, generating large amounts of heat if the mixture is vigorously stirred. The regulations are being amended to reflect this incompatibility.

10.3 Slop Disposal and Arrangements

• Slops are to be disposed of according to Regulations for the control of pollution by noxious liquid substances in bulk (IMO MARPOL Annex II). When it is necessary to dispose of slops to shore reception facilities, the ship must report estimated quantities to the Ship Operator.

10.4 Removal of Acrylonitrile from Drip Trays

• Any product that may enter drip trays when disconnecting the cargo hoses must be transferred to a slop tank or a toxic waste container by safe methods.
• Personnel must wear rubber gloves, face shields, plastic-coated clothing, and self-contained breathing apparatus (SCBA).
• Small spills may be flushed away with water.

11. HEXENE-1

11.1 Description

• Hexene-1 easily picks up oxygen and moisture, forming peroxide. Special care, as outlined in the next section, must be taken to clean, dry, and purge the tank.

11.2 Cleaning Instructions

• Tanks shall be cleaned to ethanol standard.
• Prior to loading, the tanks will be thoroughly inspected. Wall wash using Hexene-1, Hexane, and Methanol will be part of the survey.
• To prevent oxygen admission, the following measures must be taken:
• All tank openings and flanges should be sealed with silicon (if there is any doubt about their tightness).
• A rupture disk should be placed in the PV line. If possible, this rupture disk shall be supported to avoid damage to the disk.
• At the loading berth, the tank, cargo lines, and vapour lines shall be purged with high-purity nitrogen (shore supply) until an oxygen content of 200 ppm is reached.
• Before loading, the shoreline shall be filled, sampled, and analyzed. After approval, the ship's line shall be filled, sampled, and analyzed. When this sample is accepted and the first foot is loaded, loading can be resumed under vapour return.
• To avoid peroxide contamination in the hexene-1 residue in the cargo lines, such residue shall be blown back to the tank with nitrogen after loading. This includes the complete line, including branches.
• During the voyage, the tank, line, and vapour return line shall be kept under a positive nitrogen pressure of 200 KPa.
• When topping up the nitrogen blanket during the voyage, ship’s staff must ensure that no oxygen or moisture can enter the cargo tank. A permanently fixed stainless steel connection and pressure regulator is recommended to regulate the tank pressure continuously.
• Alternatively, a nitrogen bottle can be placed as close as possible to the tank with a flexible hose permanently connected to the tank and bottle. Tank and line pressure should be regulated manually.
• The tank pressure is to be monitored closely and logged every four hours, along with the cargo temperature. This log should also include the minimum nitrogen pressure before topping up the blanket.
• At discharge, the nitrogen pressure on tanks and lines shall be maintained at all times. When starting discharge, special care must be taken when monitoring the pressure in the vapor space to ensure the nitrogen regulator is functioning properly.

12. PHENOL

12.1 Characteristics

• Phenol can pose a severe health hazard and must be handled with extreme caution.
• Phenol is highly corrosive to the skin and readily absorbed through it, whereupon it can affect the central nervous system and cause damage to the liver and kidneys.
• It is also a mutagen, and there is some evidence that phenol may be a reproductive hazard.
• When heated, phenol will produce flammable vapours that are highly toxic (at just a few parts per million) and explosive (at concentrations of 3% to 10% in air).
• Phenol is a crystalline solid or a thick liquid with a sweet, tarry odour, and it ranges from colourless to pink.
• Synonyms: Carbolic acid, benzophenol, hydroxybenzene.
• IBC Code Minimum Requirement:
• UN number: 2312
• Pollution category: Y
• Hazards: Safety and pollution hazard (S/P)
• Ship type: 2
• Tank type: 2G (Integral and Gravity tank)
• Tank vents: Controlled venting
• Tank Environment: No
• Electrical equipment: T1, iiA, flashpoint exceeds 60°C
• Gauging: Closed
• Vapour Detection: Toxic vapours
• Fire Protection: Alcohol resistant foam or multipurpose foam
• Material of construction: Nil
• Respiratory and eye protection: Yes
• NFPA health hazard rating: 4 (for Phenol)
• Phenol is very easily discoloured, which happens when stored for a long time, and is accelerated by heat.

12.2 Special Arrangements for Carrying Phenol

• The Chief Officer shall make all personnel engaged in Phenol operations familiar with the procedures for dealing with accidental discharges and emergency first aid procedures, as outlined below.
• Sufficient Draeger tubes must be available before Phenol is loaded. The criteria to determine a "sufficient" number include:
• The number of tanks to be loaded
• The possibility that each tank may have to be tested at least twice before a safe entry permit can be issued
• The ROB and expiry dates of tubes already on board as held in the “Draeger Hand Book”
• The main hazard caused by Phenol is that of liquid coming into contact with eyes or exposed skin.



Note:

• Be aware of the potential lethal consequences of even a small area of exposed skin or the eyes being splashed. An exposed area of only 2 square inches has been reported as lethal.


• The only chemical antidote available, polyethylene glycol 300 or 400, must be immediately available at the manifold, along with a quantity of cotton wool. If anyone comes into contact with Phenol, the glycol must be swabbed liberally onto the affected area. The pain is intense and death can occur within 30 minutes. After swabbing, the emergency shower must be used for at least 5 minutes.
• After this minimum period, the patient should then use their own shower for a further period of time while shore assistance is requested. There is a high risk of shock, and the patient must be reassured at all times.
• MSDS must be checked, and proper PPE, as mentioned in FOM 10.10 - Personal Safety, must be worn. Cargo hazard data sheets must be posted, and non-essential personnel must be kept clear of the operating area.
• Ensure that sufficient acid spray shields are fitted to cover flanges on the manifold and hose connections according to IBC code 15.11.4 and BCH code 4.8.4.
• Preferably, have heat tracing around vent lines and PV valves. If not possible, ensure that enough live steam supply is available for melting solidified Phenol in the vent lines.
• If the vessel is to load Phenol, a ship-specific procedure and safety plan shall be drawn up and discussed with the Marine Superintendent prior to agreeing on quantities and the loading plan. The ship-specific procedures should highlight any vessel design issues in relation to the cargo's nature.

12.3 Preparation for Loading Phenol

• Prior to arrival at the load port, tanks nominated for the carriage of Phenol must be cleaned to water white standard. Some shippers might require methanol standard.
• All hose/pipe connections must be tested with high-pressure nitrogen before commencing any operations to ensure connections are tight.
• All joints must be of Polytetrafluoroethylene (PTFE), and any leaks must be rectified before commencing cargo operations.
• When configuring lines for loading Phenol, facilities must be available at the manifold to blow nitrogen through all lines used and back into all tanks loaded.
• Tanks to be loaded shall have ballast removed from underneath. Heating coils must be opened once the product has fully covered the coils.
• Stowage shall be planned to minimize the number of loaded tanks, minimizing the use of common lines (Jumper hose, “U” piece, “Y” piece).

12.4 Loading

• Phenol must be carried at temperatures within charterers' instructions, typically between +45°C and +60°C. If the cargo is presented at the discharge port at a temperature higher than 10°C above the freezing point, there will be no need to undertake prewashing.
• Loading Phenol is a closed operation.
• Heating coils must be opened once the product has fully covered the coils. A full cargo heating log must be maintained.
• The fire main must be pressurized throughout, with monitors/hoses ready at all times.
• Steam and hot water shall be available at any time during the loading operation to unfreeze lines, valves, or vent pipes.
• Heating coils for any additional low flash cargo onboard shall be blanked.

12.5 Topping Off

• Wherever possible, tanks being loaded must be topped off as quickly as possible in sequence to prevent lines from freezing.
• Loading rates to each tank must be adjusted to minimize the chances of product freezing in the lines before they can be blown.
• When tanks with individual lines and manifolds are being loaded, consideration may be given to completing and blowing each tank as a separate entity, depending on time restrictions, shore facilities, and charterers' instructions.

12.6 Line Blowing

• Effective and mandatory blowing of cargo lines must be carried out immediately upon completion of loading. In case the loading is stopped for any reason, the Chief Officer shall have the vessel prepared and ready to blow the cargo lines immediately back to the tank from the manifold.
• If cargo tanks are fitted with a drop line, great care must be taken to load part of the cargo through the pump stack simultaneously to prevent blocking of the cargo line between the delivery valve of the pump and the drop line valve.
• High-pressure nitrogen or air must be used for blowing cargo lines.
• Controlled blowing must be conducted until the line to the tank is free from Phenol. It may take 10-15 minutes of blowing each line until the lines are clear.
• Guidance: The lines can be “tapped” using a small hammer or spanner. If a clear bell-type ring is heard, the lines should be clear. A dull “thunk” indicates that product is in the line and may already be frozen.

12.7 Sampling

• A closed sampling system shall be used. Hot water/steam must be available during sampling to unfreeze a blocked sampling point.
• If discoloration has started, it will continue regardless of any action, but note that temperature control can be applied to reduce discoloration.
• At least the following samples must be retained onboard in addition to any samples for receivers:
• Shore tank(s) sample(s)
• Shoreline sample
• Start sample at the vessel's manifold
• First foot sample
• Full tank sample after loading

12.8 Venting

• Once loading has commenced, it must not be interrupted unless deemed absolutely essential by the responsible officer.
• If loading is interrupted, lines must be blown using the line blowing procedure outlined.
• Rates to individual tanks must be adjusted to facilitate quick and effective topping off, without risk to personnel, the environment, or the ship’s cargo system.
• All tanks to be loaded must have adequate ventilation. As Phenol freezes at +40°C, personnel must be made aware that there is a possibility that vent lines may become blocked should the vapour freeze.
• During loading operations, Phenol vapour will be released into the air and can fall as snow. If this happens, it should be treated as a minor spill and handled according to the COMPANY contingency procedures.
• Phenol is classified in CFR 49 as a cargo requiring vapour control, and the terminal shall be requested to provide vapour return.
• If the terminal intends to load phenol without vapour return, the Master and Chief Officer shall make a full risk assessment and ensure that people within the hazardous area are wearing maximum and relevant PPE.
• The rate of loading shall be controlled so that liquid Phenol does not get pushed up the riser with Phenol vapours.
• If the terminal intends to load Phenol without vapour control, the Master shall issue a Letter of Protest (LOP) to the terminal.

12.9 Heating and Care During Passage

• Once the lines have been blown, hoses can be disconnected and blanked. During the loaded voyage, flexible hoses shall be disconnected along with any sections of “non-permanent pipework” such as reducers, “Y” pieces, crossovers, and similar.
• There are no special carriage requirements for Phenol, other than ensuring that the cargo temperature is maintained in accordance with charterers' heating instructions.
• If no specific heating instructions are supplied, the cargo shall be kept at a temperature of approximately +55°C, or advice shall be sought from the Marine Superintendent.
• A full cargo heating log must be maintained.

12.10 Discharging Phenol

• Take care during the initial stages of discharge to ensure that vapour lines, pressure/vacuum valves, pump stack valves, deck tank sumps, and similar are unblocked by applying either external live steam or hot water, and then check that:
• Product is moving and being discharged.
• Tank ventilation is effective for the discharge rate.
• If there is any doubt, the discharge rate must be slowed down. If discharge is stopped, then dry air or nitrogen must be available immediately to blow and clear lines.
• The fire main is to be pressurized before commencing discharge and throughout all cargo/tank cleaning operations. The anchor cables can be used to bleed pressure while the system is on standby.
• Foam/water cannons are to be directed over the cargo handling/manifold area throughout the operation.
• If the cargo is to be discharged in parcels, then the following precautions must be made prior to completing a parcel:
• Nitrogen must be available to immediately blow all lines back to the tank(s) being discharged. Lines must be blown until the Chief Officer is satisfied that the lines are clear.
• Upon completion of a tank/cargo, a tank dry certificate must be issued immediately, and due notice must be given to the receiver’s representative to ensure that he/she is onboard and in position prior to completion of the cargo.
• The minimum number of tanks and lines shall be used for each parcel. Once the tank dry certificate has been issued, lines must be blown until the Chief Officer is completely satisfied that the lines are clear.



Note:

• During line blowing operations, all non-essential personnel must be prohibited from access to the deck and all personnel engaged in phenol operations must wear full protective clothing at all times. During line blowing, phenol can be blown into the air, with the result that it will fall as snow. Extreme care must be taken at all times to avoid any contact.


• Upon completion of blowing, the adjacent area shall be drenched with sea water to wash away any residual product that may remain.
• Water shall be introduced into the empty tank as soon as possible to sufficiently cover the heating coils. This can be done by either using a fire hose (without a nozzle) or a butterworth machine (without a tank washing machine).
• Once the water is in the tanks and covering the coils, the coils are to be opened. This will have two effects:
• Any ROB (residue on board) will be diluted to reduce the adverse effects of the cargo and to lower its freezing point.
• The diluted product will be heated to avoid any freezing of pump sumps and lines, enabling tank cleaning operations to be carried out.



Note:

• Extreme care must be taken when opening any access to a tank which has held phenol. All personnel engaged in phenol operations must at all times wear full protection.


• Should there be a major leakage, the area must be drenched by using the water cannon. Shore authorities and COMPANY Head Office must be advised if a major spillage occurs.

12.11 Tank Cleaning Operations

• Phenol is a category “Y” substance and depending on the discharge temperature, should be pre-washed in accordance with MARPOL requirements (Solidifying Substances). Procedures for pre-washing are as follows:
• On completion of discharge, a tank dry certificate must be issued by receivers.
• Float gauges should be raised and placed in “sea condition” to prevent damage.
• Lines must be blown with nitrogen.
• One portable washing machine must be prepared for each tank to be pre-washed.
• Water washing temperature should be at least +60°C. (Phenol becomes miscible in water at +60°C). Wash for one cycle of the machine.
• Washings must be transferred to shore reception facilities. (Pre-washing slops can be transferred to a nominated temporary slop tank while reception facilities are being prepared).



Note:

• All personnel engaged in phenol operations must at all times wear full protection.


• Once pre-washing has been completed, the Cargo Record Book must be endorsed properly, or a certificate must be attached to the relevant page.
• Regardless of whether or not tanks have been pre-washed, all tanks used for the carriage of Phenol must be tank cleaned in accordance with the requirements of MARPOL Annex II substances, as a minimum and prepared for the next cargo.
• Any instructions regarding special cleaning procedures supplied by the charterers must be followed, and the washing/cleaning procedures should be detailed in the vessel’s tank cleaning log book. The following shall be regarded as a minimum:
• Prior to washing, the water temperature shall be raised to at least +80°C, and all butterworth openings must be utilized.
• At least two complete cycles, with 3-5 drops, should be conducted to ensure that all tank surfaces are covered.
• Fresh water rinsing should follow.
• Vent, mop, and dry the tank.
• Completion of a tank entry certificate before any entry into a cargo tank can take place.

13. BENZENE OR MIXTURE

13.1 Product Characteristics

• Product safety data sheets may be available from various sources. For safety preparation, until the specific product safety data sheet can be obtained, the below information, mainly selected from the Chemical Data Guide for Bulk Shipment by Water (U.S. DOT), should be used.
• Concerning the IBC/BCH code (respective 16.2/5.2), the Master should request the specific product safety data sheet before commencement of loading.
• The safety data sheet posted must be in a language understood by the ship's Officers and Crew (English).
• A product safety data sheet for Benzene or mixtures must be posted and observed.

Typical Physical Property Information for Benzene:

Appearance	Colorless, Clear liquid, or white crystalline solid
Odour	Characteristic aromatic
Molecular Weight	78.11
Flash Point	-11ºC (closed-cup)
Freezing Point	-5.5ºC
Boiling Point	79.8 ~ 81.0ºC
Vapour Pressure	70mmHg at 20ºC
Vapour Density	2.8 (air)
Specific Gravity	0.8790 (20/4ºC)
Kinematic Viscosity	0.74cS @ 20ºC
Solubility in Water	Negligible (0.18%@25ºC)
Coefficient of Thermal Expansion	0.001215/ºC @ 20ºC
Flammable Limit	1.4% ~ 8.0% (in air)
Auto / Self Ignition Temperature	538ºC

13.2 Fire & Explosion Hazard

1. Status	Severe fire hazard. Moderate explosion hazard
2. General	Vapor/air mixtures are explosive. The vapor is heavier than air. Vapors or gases may ignite at distant ignition sources and flash back. Electrostatic discharges may be generated by flow or agitation resulting in ignition or explosion.
3. Flash point	-11ºC (closed-cup)
4. Flammable limits	1.4% ~ 8.0% (in air)
5. Autoignition temperature	538ºC
6. Extinguishing agents	Carbon dioxide, dry chemical, water, regular foam.
7. In case of fire	Follow ST&T contingency plan
8. Special fire fighting	Highly inflammable and compound produced is highly toxic. Vapors are toxic. Contact can result in blood cancer. Firefighters should wear breathing apparatus.

13.3 Health Hazard

1. Irritating Vapour	May cause respiratory tract irritation, skin irritation, eye irritation, central nervous system depression, cancer hazard.
2. Irritation from Liquid	Minimum hazard. May cause tingling sensation in long-term exposure.
3. Chemical Poisons	Moderately hazardous chemicals.
4. Odour Threshold	4.68 ppm
5. Permissible Exposure Limits/TWA	1 ppm
6. Threshold Limit Value/TWA	0.5 ppm
7. General	Repeated or prolonged breathing of benzene vapors has been associated with the development of chromosomal damage in experimental animals and various blood diseases in humans ranging from aplastic anaemia to leukemia (a form of cancer). All of these diseases can be fatal.
8. Symptoms	Slight irritation and moderate systemic effect causing dizziness, headache, and drowsiness.
9. Short Term Exposure Limit (PEL-STEL)	Can have severe systemic effects - a definite cumulative action causing headache, dizziness, fatigue, loss of appetite, irritability, nervousness, and it can cause blood disorders.
10. Exposure Procedures	5 ppm
11. Medical Management	Employees shall not be exposed to more than 5 ppm averaged over ANY 15-minute period.

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 hazards and proper precautions are taken.

Reactivity Information

1. Stability	Stable under normal conditions. Avoid heat, flames, and other sources of ignition.
2. Material Compatibility	Avoid contamination with acids, bases, halogens, oxidizing materials, and metal salts.
3. USCG Compatibility Chart	Group 32.

Spill or Leak Procedure

1. Personnel Protection	Total protection suits and breathing apparatus or air lines required.
2. Contingency Plan	Follow ST&T contingency plan.

Codes Minimum Requirements – Benzene or Mixtures

Pollution Category	Y
Hazards	Safety & Pollution Hazards
Ship Type	3
Tank Type	Integral gravity tank
Tank Vents	Controlled venting
Tank Environment	No requirements
Electrical Equipment	Special requirements
Gauging	Closed
Vapour Detection	Flammable & Toxic Vapours
Fire Protection	Alcohol resistant foam, Regular foam.
Special Requirements	See IBC Code 15.12.1, 15.17, 15.19.6, 16.2.9 and the BCH code as applies.
Respiratory and Eye Protection	Individual units are not required for emergency escape purpose.

13.4 Special Arrangements

• Arrangement Planning: In cold climates, establish a method for heating the cargo. Discharging temperature has to be at least 5ºC above the melting point to avoid pre-wash.
• Equipment Planning: Ensure to have onboard valid Draeger test tubes and/or suitable multi-gas detectors for benzene vapors detection. The boundaries of regulated areas must be indicated as NO-GO areas, and the following sign must be posted at each access to the regulated areas:
  DANGER—BENZENE REGULATED AREA CANCER CAUSING AGENT FLAMMABLE—NO SMOKING
• Ensure that there is sufficient Personal Protective Equipment available for all personnel involved with cargo operations. As minimum requirements, it must consist of the following; however, the crewmember may select a higher level of protection:
  • Pressure demand breathing apparatus
  • Full protective clothing, resistant to chemical attack

13. BENZENE OR MIXTURE

13.1 Product Characteristics

• Product safety data sheets may be available from various sources. For safety preparation, until the specific product safety data sheet can be obtained, the below information, mainly selected from the Chemical Data Guide for Bulk Shipment by Water (U.S. DOT), should be used.
• Concerning the IBC/BCH code (respective 16.2/5.2), the Master should request the specific product safety data sheet before commencement of loading.
• The safety data sheet posted must be in a language understood by the ship's Officers and Crew (English).
• A product safety data sheet for Benzene or mixtures must be posted and observed.

Typical Physical Property Information for Benzene:

Appearance	Colorless, Clear liquid, or white crystalline solid
Odour	Characteristic aromatic
Molecular Weight	78.11
Flash Point	-11ºC (closed-cup)
Freezing Point	-5.5ºC
Boiling Point	79.8 ~ 81.0ºC
Vapour Pressure	70mmHg at 20ºC
Vapour Density	2.8 (air)
Specific Gravity	0.8790 (20/4ºC)
Kinematic Viscosity	0.74cS @ 20ºC
Solubility in Water	Negligible (0.18%@25ºC)
Coefficient of Thermal Expansion	0.001215/ºC @ 20ºC
Flammable Limit	1.4% ~ 8.0% (in air)
Auto / Self Ignition Temperature	538ºC

13.2 Fire & Explosion Hazard

• Status: Severe fire hazard. Moderate explosion hazard.
• General: Vapor/air mixtures are explosive. The vapor is heavier than air. Vapors or gases may ignite at distant ignition sources and flash back. Electrostatic discharges may be generated by flow or agitation, resulting in ignition or explosion.
• Flash Point: -11ºC (closed-cup)
• Flammable Limits: 1.4% ~ 8.0% (in air)
• Autoignition Temperature: 538ºC
• Extinguishing Agents: Carbon dioxide, dry chemical, water, regular foam.
• In Case of Fire: Follow ST&T contingency plan.
• Special Fire Fighting: Highly inflammable and compound produced is highly toxic. Vapors are toxic. Contact can result in blood cancer. Firefighters should wear breathing apparatus.

13.3 Health Hazard

• Irritating Vapor: May cause respiratory tract irritation, skin irritation, eye irritation, central nervous system depression, cancer hazard.
• Irritation from Liquid: Minimum hazard. May cause tingling sensation in long-term exposure.
• Chemical Poisons: Moderately hazardous chemicals.
• Odour Threshold: 4.68 ppm
• Permissible Exposure Limits/TWA: 1 ppm
• Threshold Limit Value/TWA: 0.5 ppm
• General: Repeated or prolonged breathing of benzene vapors has been associated with the development of chromosomal damage in experimental animals and various blood diseases in humans, ranging from aplastic anemia to leukemia (a form of cancer). All of these diseases can be fatal.
• Symptoms: Slight irritation and moderate systemic effect causing dizziness, headache, and drowsiness.
• Short Term Exposure Limit (PEL-STEL): Can have severe systemic effects, a definite cumulative action causing headache, dizziness, fatigue, loss of appetite, irritability, nervousness, and it can cause blood disorders.
• Exposure Procedures: 5 ppm
• Medical Management: Employees shall not be exposed to more than 5 ppm averaged over ANY 15-minute period.

Reactivity Information

• Stability: Stable under normal conditions. Avoid heat, flames, and other sources of ignition.
• Material Compatibility: Avoid contamination with acids, bases, halogens, oxidizing materials, and metal salts.
• USCG Compatibility Chart: Group 32.

Spill or Leak Procedure

• Personnel Protection: Total protection suits and breathing apparatus or air lines required.
• Contingency Plan: Follow ST&T contingency plan.

Codes Minimum Requirements – Benzene or Mixtures

Pollution Category	Y
Hazards	Safety & Pollution Hazards
Ship Type	3
Tank Type	Integral gravity tank
Tank Vents	Controlled venting
Tank Environment	No requirements
Electrical Equipment	Special requirements
Gauging	Closed
Vapour Detection	Flammable & Toxic Vapours
Fire Protection	Alcohol resistant foam, Regular foam.
Special Requirements	See IBC Code 15.12.1, 15.17, 15.19.6, 16.2.9 and the BCH code as applies.
Respiratory and Eye Protection	Individual units are not required for emergency escape purpose.

13.4 Special Arrangements

• Arrangement Planning: In cold climates, establish a method for heating the cargo. Discharging temperature has to be at least 5ºC above the melting point to avoid pre-wash.
• Equipment Planning: Ensure to have onboard valid Draeger test tubes and/or suitable multi-gas detectors for benzene vapors detection. The boundaries of regulated areas must be indicated as NO-GO areas, and the following sign must be posted at each access to the regulated areas:
  DANGER—BENZENE REGULATED AREA CANCER CAUSING AGENT FLAMMABLE—NO SMOKING
• Ensure that there is sufficient Personal Protective Equipment available for all personnel involved with cargo operations. As minimum requirements, it must consist of the following; however, the crewmember may select a higher level of protection:
  • Pressure demand breathing apparatus and full protective clothing, resistant to chemical attack5: in areas where the airborne concentration of benzene is expected to be greater than 0.25 ppm.
  • Personal Protective Equipment (PPE): eye protection, impervious gloves and a protective apron should be readily available to crew members while sampling and gauging or when skin contact with the cargo is likely.

13.5 Preloading and Loading Preparation for Loading

• If it is not specified otherwise, the tank must be cleaned to "Visual Water White Standard" and free of any residues from previous cargoes, chlorides, and any other foreign matters.
• Depending on cargo heating requirements during the voyage, heating coils shall be tested with the relevant heating medium or blinded if no heating is required.
• All openings leading from the outside to the accommodation and to the engine room should be closed and kept closed during these operations. Only one door on the windward side/nearest to the cargo control room is to be used as an access.
• All doors inside the accommodation shall be kept closed during the operation.
• The ventilation to the accommodation shall be stopped/re-circulated and the fire flaps kept closed.
• The crew working on deck shall wear appropriate protective equipment.
• Only work related to cargo handling is allowed on deck.

Tank Acceptance Requirements

• All shore and ship cargo lines and tanks are to be presented clean (residual free), dry, odor free, and rust free, with good gaskets. Heating coils are to be blown clear and dried with N2, and blanked off.
• Stainless Steel or Coated Tank: Either, carrier to verify suitability of coating for product. Prior Cargo Restrictions.

13.6 Loading

• Benzene accumulates static charges during product transfer operations. The flow rates with which the product is transferred affects the amounts of static charge generated. During the initial stages of loading into each individual tank, the flow rate in its branch line should not exceed a linear velocity of 1 metre/second.
• Whenever a vapour emission control system is available ashore, vapours displaced from the tank during loading should be returned to that system (vapour return). Ships should therefore be fitted with piping systems suitable for vapour return.
• All cargo-related measurements (e.g., ullage, temperature, and sampling) should be carried out in a closed mode to minimize the risk of exposing the crew and shore personnel to harmful vapours. When this is not possible, personal protection equipment should be worn.

13.7 After Loading

• Special precautions must be followed when sampling and gauging of static accumulator cargoes. A relaxation time of 30 minutes after completion of loading is generally considered sufficient.

13.8 Discharging

Pre-discharge Arrangements

• All openings leading from the outside to the accommodation and to the engine room should be closed and kept closed during these operations. Only one door on the windward side/nearest to the cargo control room is to be used as an access.
• All doors inside the accommodation shall be kept closed during the operation.
• The ventilation to the accommodation shall be stopped/re-circulated and the fire flaps kept closed.
• The crew working on deck shall wear appropriate protective equipment.
• Only work related to cargo handling is allowed on deck.
• Gauging and sampling will be done by the receiver's surveyor similarly as done at loading.

13.9 Tank Cleaning and Slop Disposal

Tank Cleaning

• There is a relatively high and hidden risk of contamination, detectable only by Gas Chromatograph analysis. However, Ultra Violet (UV) testing onboard may also give reasonable indications of Benzene concentrations at higher levels higher than 5ppm. Although these products are generally considered as being easy cargoes to clean, tests show that the complete removal of residues from tank linings, including Stainless Steel surfaces, requires a considerable amount of heat (hot water).
• To minimize liability, the following should be considered: If possible, the following cargoes should not be loaded in tanks that last contained Benzene or Benzene mixtures:
  • Light Alcohols (Ethanol, Isopropyl Alcohol, Normal Propyl Alcohol)
  • Glycols (Ethyl, Propyl, Diethyl, Voranols, and Polyols)
  • Mineral Oils (Medicinal Oils, White Oils, Whiterexes, Arco Primes, Baby Oils)
  • Glycerine (especially USP grade)
  • Paraffins (Hexane, Isopars, Expars, Paraffin Waxes (especially food grades))
  • Membrane caustic
• Close dialogue must be maintained with the Charterers and Office to fully explore alternative stowages. If alternative stowage is not possible, the following wash times should be used:
• Zinc lined tanks - 1 hr ambient temperature water wash (but minimum 5°C above the melting point of the cargo/product to be washed) and a minimum 6 hours at a very hot 80°C wash
• Stainless Steel lined tanks - 1 hr ambient temperature water wash (but minimum 5°C above the melting point of the cargo/product to be washed) and minimum 4 hours at a very hot 80°C wash
• Epoxy Lined tanks - should be avoided, but if needed then a procedure should be discussed and agreed, on a case-by-case basis, between the ship, Office, and the commercial operator.
• It must be clearly understood that if a temperature greater than the boiling point of the product (80ºC) cannot be reached in the tank for any reason (i.e., due to max. heat adjacent limitations or tank cleaning water temperature limitations, etc.), then B-Solve spray or circulation followed by warm water washing may be employed. Office must be consulted immediately for additional/alternative tank cleaning methods.
• In all the previously mentioned cleaning procedures, regardless of which is used, the heating coils must be blown out during the tank cleaning process. Purging and/or flushing of cargo pump cofferdam(s) must be considered. Hot water flushing or steaming all vapour, cargo, stripping lines, etc., must be carried out as part of the tank cleaning process.
• Special precautions should be taken with regard to the cleaning of gaskets, which are sources of potential contamination if not attended to correctly.

13.10 Slop Disposal and Arrangement

• The slops are to be disposed of according to: Regulations for control of pollution by noxious liquid substances in bulk, IMO, MARPOL, Annex II.

14 OILS AND FATS

14.1 General

• Master and Chief Officer shall ensure that the Free Fatty Acid (FFA) content does not increase substantially during the voyage.
• Prolonged contact with mild steel may result in oxidation and increased FFA content and must be avoided.
• Similarly, oils and fat must not be allowed to solidify, which may happen if these products are in contact with side hells and stiffeners making circulation impossible.
• Parcels shall not be stowed commingled without having received loading orders for such stowage to take place. Parcels having different FFA shall not be loaded or discharged using the same line without the express approval of the Marine Superintendent.

14.2 Cargo Discharge Sequence for Oils & Fats

Where one pump is used to discharge more than one grade, the unloading sequence shall be planned to handle the higher-grade parcel first, where possible. The two main factors which control the FFA content and therefore the cargo quality during carriage are:

14.3 Loading and Discharging

• Drop lines shall be used for loading oils and fats.
• Oils and fats delivered to the tank may contain a lot of air, which will give the oil or fat an incorrect specific gravity, and aids oxidation. Avoid loading overall (Splash filling) which increases this problem.
• Lines shall be cleaned immediately after loading to prevent cargo solidifying in the lines.
• Similarly, cargo lines shall be steamed back into the tank as soon as possible after discharging. The steam blowing process shall be repeated to ensure all residual vegetable/animal oil has been removed.
• Air shall be used for blowing through semi-dry and non-dry vegetable oils instead of steam.

14.4 Loading Precautions

14.4.1 General

Cargo tanks must be cleaned to a very high standard and be dry for loading vegetable oils and animal fats. Transportation and carriage of vegetable oils are regulated by regulatory bodies as well as the Fats and Oil industry itself. These are FOSFA, EU-93/43, and NIOP. Accepted cargoes list is included in the annex.

14.4.2 Free Fatty Acid of Product (Max. %)

FFA values of various typical products are shown in the table below:

Product	FFA (%)	Product	FFA (%)
Castor oil	2.0	Tung oil	4.0
Coconut oil (crude) = Philippines	2.5	Palm oil (crude)	5.0
Coconut oil (crude) = Papua	Less 1.0	RBD PO & NBD PO	0.1
Corn oil (crude)	3.0	RBD PL & NBD PL	0.1
Corn oil (refined)	0.2	RBD PS & NB PS	0.25
Cotton seed (refined)	0.5	Spilt Palm Stearin	Min. 95
Cotton seed (semi-refined)	0.175	Palm acid oil	Min. 50
Ground nut oil (crude)	2.0	Palm acid oil, distillate	Min. 70
Ground nut oil (refined)	0.175	Shea nut butter	2.0
Rape seed oil (crude)	2.0
Rape seed oil (refined)	0.175
Rape seed oil (erucic acid)	2.0
Rice bran oil (crude)	17.5
Rice bran oil (semi-refined)	2.0

15 PROPYLENE OXIDE

Refer to CTM 9.10 A2 – Carriage and Handling of Propylene Oxide.

16 REFERENCED FORMS AND CHECKLISTS

No forms or checklists are referenced in this document.

17 APPENDICES

• CTM 9.10 A1 Guidelines for the carriage of blends of petroleum oil and bio-fuels
• CTM 9.10 A2 – Carriage and handling of propylene oxide
• CTM 9.10 A3 Styrene Monomer and polymerising cargoes