4

MATERIALS Iron, steel

4. 01

Mild steel and high tensile steel is, and will continue to be the most important material in the building of chemical tankers and their cargo tanks. Steel is attacked by only a few products, mainly acids and, of course ballast and washing water. Steel itself contaminates very few products, one of them being high purity caustic soda. Rust, however, creates many problems with cargo contamination. Rust may contaminate a product in the form of minute particles staying suspended in viscous heavy liquids such as glycols and caustic soda. Rust may accelerate polymerization in polymerizable products. Rust will be soaked in with remains of previous cargoes, mainly from heavy oils, which will contaminate the next cargo. Rust will, above all, render tank cleaning much more difficult, cause delays and perhaps cargo claims. ue to the above reasons steel is practically never used in chemical tankers without a protective coating, see !. "#. $oating techniques have advanced greatly in latter years. Still, however, one does not dare to use coatings for products, which are really aggressive to steel, e g acids %such as phosphoric acid&. 'ne has to reckon with coating defects where corrosion will start. 'ne exception to this is rubber linings, which have been in use a long time with corrosive cargoes. (or information on a particular product)s sensitivity to steel steel and rust see ref %*&, +ppendix , and #. -enerally speaking, steel is resistant to alkalies, even in high concentrations %caustic soda, ammonia&. 4.02 Stainless steel Stainless steel has increased greatly in use as tank material in later years. .he motif is not only a better chemical resistance but primarily it provides for a greater ease in tank cleaning and inspection. .hus cargo contamination hazards can be reduced. .he stainless properties are due to the formation of a very thin, passive layer of chromium oxide on the surface. .he care of stainless steel tanks aims at maintaining this protective film intact. Stainless steels possess a number of advantageous proper ties, rustproofness, however, is not guaranteed. ,t depends on the correct treatment of the tanks and on what products carried. + short review may be of interest. .he commonly used stainless steels have the following typical compositions/

0ow carbon contents are required to make the steel corrosion resistant near the welds. $arbon tends to bind chromium to form chromium carbide in the heat affected zone near the welds, thus reducing the corrosion resistance locally. .he addition of titanium has a neutralizing effect on this process and therefore slightly higher carbon contents can be tolerated. .he addition of small amounts of nitrogen increases the tensile strength of the steel considerably. Such steels are often used in more highly stressed parts such as corrugated bulkheads sub1ected to corrosion from both sides, where weight reduction is at a premium. -eneral corrosion of stainless steels from corrosive cargoes such as phosphoric acid is of a low intensity and can therefore be disregarded. 2itting corrosion might cause severe damage. .o avoid this happening it is important to choose the correct type of stainless steel. -enerally speaking high molybdenium contents is beneficial in this respect. 2ittings may take the shape of small holes, *34 mm in depth and diameter to begin with. +t times they are almost hidden below the surface of the steel with an 5entrance hole5 of only a few tenths of a mm. with a cavity of *34 mm below. .hey are therefore sometimes very difficult to detect. So called dye3penetrant tests are useful for detection when one knows approximately where to look for defects. 2itting may develop in a generally corrosive surrounding, especially when the surface is disturbed or when some extra chemical aggressive age.nt is present such as/ 3 chlorides %seawater, 5salt5&. $ontents above some *""34"" ppm are generally dangerous when together with some other corrosive agent such as phosphoric acid. (luorides have a similar effect. 3 particles of iron3or other materials on the surface 3 craters or pores in weld deposits 3 weld slag or slag from rolling mill 3 surface defects, micro cracks, rough surfaces 3 lack of oxygen renders formation of chromium oxide difficult 3 high temperatures %above ca !""$ corrosion rates in crease rapidly& $revice corrosion may occur in narrow spaces where the corrosive agent can enter but without circulation, with a lack of oxygen as consequence. .ypical locations/ - under bolted connections - under cargo sediments - under paint on a stainless steel surface. .he following rules for maintenance of stainless steel apply/ *. 6eep chlorides away. +void seawater in the tanks and rinse with freshwater carefully after seawater washing. Seawater must never be permitted to dry up and leave salt crusts on the surface. 6eep the hatch covers closed and the airpipes protected to prevent seawater or a saline atmosphere entering the tanks. 2referably change footwear before entering a tank when at sea. 4. Remove any particles or sediments such as rust, particles from grinding operations, cargo sediments %phosphoric acid&, 5scale5. $argo remains to be removed as soon as possible after discharge. 7. Surface finish. .ank surfaces to be kept bright and free from scratches. .his means3that possible corrosion or other mechanical defects should be ground and polished to the original finish. 8ormally grinding disc 5grain 9"5 can be used, followed by a final operation with 5grain *4"5. 0ocal pittings of substantial depth can be welded, minor pittings ground away. !. ,nspect for corrosion after each cargo, especially tank bottoms and under deck. ,n order to avoid salt crystals forming on the tank bottom *"34" cm fresh water is sometimes kept in the tanks on the ballast voyage.

#. $leaning can normally be carried out with all common cleaning agent:s such as 5emulsifiers5, 5solvent cleaners5 and alkaline cleaners as well as caustic soda. ;. Stainless steel tanks are sometimes passivated by application of *43 *# < nitric acid %=8' 7& . .his acid is strongly oxidizing. .he procedure assists in building up the passive chromium layer on the steel, thus increasing its chemical resistance. 2assivation is normally carried out after tank surface repairs in order to assist the normal passivation in air. ,f aggressive cargoes are to be loaded within 4! hours all repairs must be passivated. ,n practice 5passivation5 with nitric acid is often used for the removal of dis3 colorations and particle contaminations on the surface. ,n factlit is being more used as a thorough cleaning agent than a passivating chemical. 2assivation is normally carried out with a brush or, for a whole tank, by spraying, +fter *"34" min the acid should be washed off with large amounts of fresh water. ,M2'R.+8./ 8itric acid gives off nitrous gases which are very toxic %with delayed effects&. >entilate completely and use breathing masks for larger areas in confined spaces? .he atmosphere can be tested for nitrous gases by means of test tubes, see 7. *". @se protective clothing and goggles. 8itric acid is usually available in ;" *Ao concentration. Be careful/ spills may cause self3ignition of organic matter. See also ref Ci& for safety precautions with nitric acid. D. 2ickling is the toughest way of cleaning stainless steel. .his method is used for the removal of welding slag, oxides and discolorations from welding or discoloration from cargoes. 2ickling paste, consisting of, among other components, nitric acid and hydrofluoric acid shall be applied with the same precautions as nitric acid above. 2ickling should be followed by passivation with nitric acid. 2ickling involves a lot of work and can only be used on relatively small areas, unless carried out by specialists. 4.03 Cuprous alloys $opper and its alloys corrode in many cargoes and may contaminate them, e g styrene, phenol, vinyl chloride, aniline, ammonia solutions etc. $heck your cargo against information given in e g the ,$S3-uide ref %*&, %!& and %#& or +ppendix * and #. 2articularly aggressive are the ammonia compoundsE they cause inter 3crystalline corrosion of cuprous alloys very rapidly. .he ob1ect in question disintergrates very soon. =eating coils of cuprous alloys are attacked by caustic soda %8a'=& after being used a long time. But for a limited number of voyages no serious problems seem to arise. +s a general rule in chemical tankers one tries to replace cuprous alloys with stainless steel %+,S, 7*; or 7*D&. 'ne must remember, however, that stainless steel easily scores against stainless steel in sliding contact %in valves etc& and design accordingly, using also other materials. 4.04 Magnesium an aluminium, alloys

+lloys of magnesium and aluminium should never be used in the cargo tank area, due to their poor corrosion resistance in such environments. +s sacrificial anodes these alloys are frequently used. .hey are severely attacked by caustic soda. Methanol will be severely contaminated by magnesium. +ny anodes should be removed before loading these cargoes. $heck cargoes against ref.,%*& or other information. .here seems to be a belief that +lAMg alloys are spark3proof materials, suitable for tank cleaning equipment etc. .he truth is the opposite/ 5light alloys5 are considerably more prone to cause incendive sparks than steel ob1ects. Fhen an ob1ect fall3s down into a tank light alloys oxidize at the point of contact, thus adding a reactive energy to the kinetic energy released. 5=ot5 sparks are created instead of 5cold5 sparks, which are created by steel ob1ects falling down. +s a flammable mixture requires a certain minimum amount of energy to trigger off an explosion it follows that 5light alloys5 are considerably more dangerous. .herefore/ do away with tank cleaning gear of light alloys?

,n this connection it can be mentioned that so3called spark free tools are no longer particularly recommended. .ests have shown that steel tools are equally safe, see ref %G&. 4.0! Tan" #oatings

+ modern chemical tanker has all her cargo tanks coated unless they are made of stainless steel. .he main reasons for coating are/ easier cleaning and less risk for cargo contamination. .he durability of properly applied and maintained coatings may be ten years or more. 'n the other hand one mistake in cargo selection may totally ruin a coating. ,t is a matter of knowing the limitations and possibi lities of each type,or even of each make, of coating. =ere the chemical build up of coatings shall not be elaborated, only the physical properties as regards resistance and application. Hvery paint manufacturer has his own resistance list stating approved cargoes, temperature and time limitations etc. $ontact the maker if in the slightest doubtE mistakes may turn out to be very costly. Many coating manufacturers give some sort of guarantee for the first two years after application. Hpoxy coatings generally possess a good resistance against alkalies, seawater, wine, vegetable oils, crude oils, gas oils, lub oils, 1et fuels, gasoline and also weak acids %as in free fatty acids in vegetable oils, but acid value should not exceed 4"3!"&. Hpoxy ha s limited resistance against aromatic hydrocarbons %5solvents5 such as benzene, toluene&, certain alcohols %e g methanol&, ketones %acetone& and some esters. Hpoxy is sometimes indicated as resistant also to stronger acids. .his may be correct, but as an applied coating one must count on 5holidays5 in the film, thus making epoxy unsuitable for really corrosive liquids. Hpoxy coatings which have been stressed beyond their chemical resistance with strong solvents tend to softenE test with your nails. ,n such a case the coating must be given ample time to 5weather out5 trapped solvents and recover its hardness before being sub1ected to cargo or water again. o not try to speed up the recovery by application of heat? .he top skin of the coating may then first harden, leaving trapped solvent underneath, with flaking as a consequence. >entilate with a good turbulence in all corners of the tank. =ardness of epoxy coatings can be established by means of a standardized test using pencils of different hardness as a reference %Sw standard S,S *9! *9D&. +dhesion of a coating to the steel is also reduced if it is overstressed by a cargo of strong solvents. .here are standard test methods for the determination of adhesion by means of glued3on tablets, which are then pulled off with a recording of the necessary force. Hpoxy coatings should normally not be heated above ;" 3%9"& degr.$ during tank washing, steaming etc, uring the loaded voyage lower temperatures should be kept. Hpoxy tar coatings. are made up from epoxy with an addition of coal tar. .hey are excellent against seawater and crude oils but should never be used in chemical tankers, 0ight hydrocarbons of moderate solubility such as 1et fuels, gas oils, gasoline may cause the tar to leak out, which may contaminate the cargo. Iinc silicate coatings particularly those of inorganic type, are very resistant against strong solvents and normally tolerate higher temperatures than epoxies. .ypical products are/ aromatic hydrocarbons %benzene, xylene etc&, alcohols, ketones. Jet fuels may suffer zinc 5pick up5 from the coating to an extent which is considered a contamination. .herefore/ check with shippers requirements. Iinc silicates are not resistant against acids or alkalies. .he p= value of the cargo should be within the range #, # 3*", # %neutral p= D, "&. .his means that some molasses %slightly fermented 3 low p=& may attack zinc silicates, as well as high contents of free fatty acids in vegetable or animal oils/ Iinc silicate coatings may under such circum stances cause zinc pick up into the cargo. .hey are therefore not normally suitable for edible oils for human or animal consumption. Remember that the contents of free fatty acids, and thus also the aggressivity and zinc pick up, may increase during transport. $ertain coatings have -overnmental approval for edible oils, check for p=3limitations in such cases. Iinc silicates are not suitable for long time exposure to seawater, the life span will be unduly reduced.

+fter carriage of molasses in zinc silicate coated tanks a thorough cleaning should be carried out as soon as possible. Sour cargo remains on the tank bottom may damage the coating. Iinc silicates are only partly resistant to chlorinated compounds %e g carbon tetrachloride, ethylene dichloride, trichlorethylene&. ,f the water content is high hydrochloric acid may develop, which will attack the coating. ,n a similar way hydrolyzable hydrocarbons such as esters, acetates and halogenated compounds may .attack the cargo. ,f, however, the product is guaranteed dry and the cargo tanks and piping are completely drained and dried these products can be carried. +lkaline tank cleaning agents %caustic& should never be used in zinc silicate coated tanks. $onsiderable damage can be doneCin one single cleaning operation. Iinc silicates stand well up against other cleaning agents such as 5solvent cleaners5 and 5emulsifiers5 unless they have alkaline additives/ $heck first with the maker of the cleaning product? ,f a zinc silicate coating has been attacked one can often observe a thin layer of white dust on the surface, or the coating gives a porous appearance. ,nform the 'wners at onceE it may be that the last cargo was off specification and caused the damage. 2henolic resins are a recent addition to the family of tank coatings. .hey have a wide resistance list including strong solvents which the epoxies do not tolerate3 +t the same time the phenolics accept about all of the products that zinc silicates tolerate. .his type of coating is likely to gain further application on board. 2olyester coatings have poor resistance to solvents but are fairly resistant to weak acids and alkalies. .hey are not used on board in chemical tankers to any extent. Maintenance of tank coatings means, above all, not to sub1ect the coatings to non3permissible cargoes. $heck with maker:s recommendations. 0imitations as regard p=3values, max temperatures and max permissible storage time on board must be followed. 0et epoxies regain their hardness if softened. -enerally it is not worth while to recoat an epoxy coated tank on top of an old coating, the risk for a poor bond is too great. Minor damaged areas can, with a certain degree of success be recoated. .he area must first be degreased well. .he area should then be ground to a bright steel finish with a rotating grinder, grain 9" to *4", with an even transition to the coating. * 3 4 coats of primer plus 7 3 ! finishing coats may be necessary in order to build up the proper film thickness %4""37"" microns&. .he tank wall may have to be warmed up %preferably from behind& in order to insure that there is no risk for condensation on the surface. ,f possible the, tank wall should be warmer than the tank atmosphere. (or application of coating on a whole tank the steel bulkheads must be properly sandblasted %non marine origin sand&, normally to the internationally known standard Sa 4 *AK. 4.0$ Ru%%er lining

,n recent years a number of ships have been fitted with rubber lined tanks, for the transport of phosphoric acid, waste acids and hydrochloric acid. .he mild steel surfaces to be lined should be prepared by grinding away rough weld beads, surface defects, weld splatter etc. .hen comes sandblasting to 5bright metal5 %Sa 4 *A4 3 7&, priming with a rubber glue and an application of a contact rubber glue. .hereafter the uncured rubber is applied in wide sheets and pressed on by means of hand rollers. .he rubber is usually !3; mm thick with reinforcements where mechanical wear may occur, such as hatches etc. .he rubber is vulcanized by heating with steam or hot water for a period of *#37" hours. Synthetic rubbers may have a curing accelerator added and will vulcanize at normal ambient temperature %4"37" degr. $& in a few weeks. 8atural rubber has been used in ships for phosphoric acid. But chloroprene %neoprene& synthetic rubber is a more usual choice on board. ,t has a much better resistance to sun radiation, oils and ozon,

$hloroprene is, however, more expensive and is somewhat more difficult to apply. $hloroprene is resistant to strong acids %not sulphuric acid& and strong alkalies such as caustic soda. ,n some cases chloroprene lined tanks have been used for backhauls with fuel oils. .his rubber will, however, not tolerate light hydrocarbons. Butyl rubber has a very good chemical resistance but is stiff and hard to apply. -reat caution must be exercised so that the rubber will not be sub1ected to mechanical damage due to falling ob1ects, tools etc, Rubber lined tanks should have a minimum of fittings such as brackets, ladders, internal piping etc which can create weak spots. Steel piping, including bends, can be rubber lined. .he pipe diametres should be chosen somewhat liberally in order to keep liquid velocities relatively low. Membrane types of valves as well as pumps can be lined with hard rubber. +s heavy wear may occur on these parts the use of stainless steel is, however, recommended. .he advantage of having a pure rubber lined system with regard to a possible high contents of chlorides in the product will then, however, be lost, see !."4. Rubber linings are tested for pores and defects by means of a high voltage tester at *" """ > %chloroprene& and 4" """ > %natural rubber&. .o check the progress of curing or aging a Shore urometer is used. Shore tanks are sometimes lined with 2>$ %poly vinyl chloride& sheets glued into place. But this technique does not seem to be sufficiently developed for use on board ships. !."D -askets and packing Fhen 2.(H %polytetrafluor ethylene, trade names/ .eflon, (luon, =ostaflon .(& came on to the market a few Lears ago it solved many gasket problems. .his material is resistant to all likely chemical cargoes and all common temperatures on board. .he 2.(H has some very typical properties/ it is expensive, has a low frictional resistance and a low thermal conductivity, does not adhere to other materials and yields or 5creeps5 when under pressure. 2.(H as a gasket in flange connections should either be reinforced %asbestos or glass fibres&, contained in a grove %maleAfemale& or used as a relatively thin envelope around a core of more conventional gasket material. 5$reep5 can then be controlled. 5Blue5 asbestos generally gives better chemical resistance against acids %p= *3!& than 5white5 asbestos. ,n 5envelope5 gaskets the cargo comes into contact with 2.(H only, which is an advantage. ,t is an advantage to use 2.(H packings in pump and valve spindle gland boxes. But remember that the bottom clearance between spindle and housing may have to be less than usual as the packing will have a tendency to creep out this way. +lthough 2.(H will solve most problems one must remember that common, and cheaper, materials will often suffice. ,f an existing oil tanker is to carry strong solvents %e g aromatics, ketones etc& flange gaskets of asbestos3 reinforced synthetic rubber will usually be acceptable. (lange gaskets of synthetic rubber3asbestos will normally stand up against strong solvents, alcohols, strong alkalies %caustic& and acids. ,f in doubt, check with the maker. Hxpansion glands in cargo piping and valve spindle glands, however, should be repacked with 2.(H3asbestos packings. Rubber gaskets are not suitable for oils or solvents. Rubber is suitable for phosphoric acid. $hloroprene rubber %8eoprene& is resistant to caustic soda and ammonia solutions. $arbon fibre spindle packings are sometimes used in high speed pump glands. .hey are expensive but have the advantage of low friction, chemical inertness and high thermal conductivity.

8itril and fluor %>iton& rubber have a very good chemical resistance, see 7. "4, to strong solvents as well and are used particularly in '3rings for stem seals in valves. See also resistance table in $hapter 7. "4.

&IRE 'R(TECTI()

(ire prevention is one of the most essential safety measures on board a chemical tanker. iscipline is needed in the daily routines. Fatch out for obvious things such as/ - look out for all leaking flanges, valve and pump glands - keep pump room bilges free from cargo spills - see to it that steam pipe insulation does not get soaked with oil or cargo - check cargo tank and pump room atmosphere for cargo vapours before starting any work there - do not steam a cargo tank simultaneously with washing - use flame3proof lights in cargo tanks and pump rooms - check pump glands and bearings regularly for heating - cigarette lighters in the cargo tank area to be forbidden - observe cargo vapour release during loading and take action if vapours reach accomodation areas - check cargo pump glands for heating - take active part in safety 3drills and get acquainted with all the safety equipment - instruct newcomers on board on safety procedures - get to know your ship, cargo handling gear etc. .he formal responsibility for surveillance of the fire fighting equipment normally rests with the respective 8ational +uthority, but is in some cases delegated to the $lassification Society. ,t rests with the 'wner and the Master to keep all equipment in order and to provide additional means for any cargo not covered by the intent of the Rules of the 8ational +uthority. .he ,M$' 5Bulk $hemicals $ode5 ref %4#&, $hapter ,,,, see +ppendix ;, gives some general guidance on necessary equipment on board and indicates the best means for extinguishing fires for a number of cargoes. Similarly the ,$S .anker Safety -uide ref %t& gives more detailed information on the choice of extinguishing method to be used for the individual cargoes Several methods of extinguishing fire can be used. Fithout going into more complicated details let us list the most important aspects of the matter of fire fighting in the cargo area on chemical tankers/ !.01 *ater e+tinguis,ing +ll ships are fitted with means for fire fighting with water. +lthough not ideal, water can be used on fires in a ma1ority of chemical cargoes, the advantage of course lying in its abundant supply. Fater is, however, not very effective in extinguishing fires in very gassing cargoes such as naphta, gasolines or liquified gasesE it may, however, then be used as a cooling medium in connection with dry powder or other methods of fire fighting in order to avoid dangerous 5back flash5, see #. "7. Fater should be applied to the base of the fire by means of water fog 1ets, water pressure preferably not lower than G kpAcm 4. .he fog serves as an excellent heat radiation shield in front of the. operator. 8ever direct a solid 1et of water on to a burning liquid surface, the effect will only be that burning liquid is splashed around, thereby making the fire bigger. :Fater fog shall be applied with a strategy of chasing the fire succesively away from the operator. .he fog may be swung from side to side to cover a wide front of attack. o not apply water fog on top of foamE it will cause the foam to disintergrate and may possibly in so doing ex3 pose the surface of the flammable cargo to the risk of a back flash. ,t is a good practice to have water hoses with fog 1ets connected to the fire main on deck during cargo handling. .he ,M$' $ode ref %4#& advices against water for most products in the relevant 5Summary of minimum requirements5. .his list, however, is meant to emphasize that other extinguishing media are a first choice and are to be provided on board. o not hose water into conc sulphuric acid, an eruption of liquid may occur? !.02 &oam e+tinguis,ing

(oam extinguishing is provided on many chemical tankers and on a ma1ority of modern large crude oil carriers. 'f all the extinguishing methods in the ,M$' $ode foam is preferred, but the use of dry powder is generally accepted as an equivalent method. Fater soluble chemicals, e g acetone, alcohols, have a tendency to break down conventional foams and render them in effective. $hemical tankers should therefore be provided with alcohol3 resistant foam % 5alcohol foam5&. 'n the data sheets in the ,$S3.anker Safety -uide, $hemicals, ref %*& it is especially stated for every product if alcohol3 resistant foam is a 5must5. =eavy foam %waterAair ratio abt */*#& is in modern tankers distributed by means of several foam guns which can cover the entire deck area, by means of portable 1ets or by means of long portable pipes. .he latter are intended to be used for the introduction of foam into a tank on fire without risk for the foam to dip underneath the liquid surface. (oam has a limited extinguishing effect on very gassing cargoes/ the

gases penetrate the foam and burn on top of it. (oam is a good method for fire prevention/ a deck area or a free cargo liquid surface can be protectively foam covered if there is a danger of fire. ,f a liquid surface is to be foam covered/ direct the foam onto a bulkhead or other vertical surface and let it spread from there and float out to cover the entire liquid surface. .he foam operator may have to be shielded against heat radiation by means of a water spray. Medium density foam %waterAair ratio abt */4""& is used in enclosed spaces such as pump rooms. Medium density foam can be produced very simply in fixed distribution 1ets under deck, in e g a pump room, by using the e1ector power of the water stream to draw air into the water foam mixture. Medium density foams are intended to cover the bottom part of a compartment. .he installation is very simple and relies on starting the fire3pump only. 0ight foam %waterAair ratio */4"" 3 */*"""& is only used in enclosed spaces such as engine and pump rooms. ,t is usually produced by means of a water driven fan which blows up the foam mixture. .he foam is intended more or less to completely fill up the compartment in question. 0ight foam is sometimes used as a preventive blanketing medium when 5hot work5 %e g welding& has to be carried out in a cargo tank, which may not have been possible to clean perfectly. .he whole tank bottom is then foam covered, leaving only the work location free. 'f course the tank has to be guaranteed gas free before starting hot work. Similarly neighbouring tanks can be protected before welding is started on bulkheads. 5.03 Dry powder extinguishing Many new chemical tankers use dry powder extinguishing method in the cargo tank extinguishing area. ry powdersystem as the main fire fighting

.here are to be found centralized powder systems with possibilities of discharging several thousand kgs of powder. Release boxes and hose f eels are strategically located on deck so that any point can be reached by two hoses, each being usually max 4# m length. 'n smaller vessels self3contained powder containers of *"""37""" kgs are located in small deckhouses. +s mentioned above the ,M$'3$ode accepts dry powder as equivalent to foam. limitations, which are explained below. ry powder has decided

.he extinguishing effect of dry powder originates mainly from an inhibiting effect on the combustion. .he smothering and cooling effects are small. ry powder has a particularly good extinguishing effect on larger volumes of burning gases and strongly vapourizing liquids, as compared with other means of fire fighting. But it has virtually no cooling effect on any steel, cargo liquid or other matter that has become heated from the fire. 'nce the flames have been thrashed out with dry powder there is a great risk for a fire back flash which can be more violent than the original fire. +t a ma1or fire therefore, the fire area should be cooled down with water fog as much as possible prior to application of powder. Fater cooling must be continued after the flames have been extinguished ,f a fire can be fought immediately after its outbreak and only little heating has occurred one should of course immediately start with dry powder, not awaiting water fog assistance. $ommon types of dry powder have a tendency to break down a foam layer. .herefore the two methods should be avoided being used together. Some new powders are claimed not to have this deteriorating effect on foam. +lways place two dry powder extinguishers at hand on deck aft of the cargo manifold, when loading Aunloading. !.04 -Total .loo ing- system .or pump rooms. Inert gas .or .ire prote#tion

,, Many tankers have a3$'4. Mtotal flooding5 system for the cargo pump rooms. .his is a most effective method for extinguishing a fire in a closed compartment. $ertain dangers, however, are involved - make sure the room has been evacuated before admission of $' 4: 8o one will have a chance of escaping once the gas has been admitted. the released $' 4 may assume a strong electrostatic charge which may cause incendive sparks. .his is of no consequence if the room is already on fire, but if the room is to be inerted with $' 4 as a preventive, measure this should only be done knowing that the room is gas free. 0ately halogen gas total flooding systems have been installed on a trial basis. .his gas does not possess the above disadvantages and is easier to install. ,nert gas in the cargo tanks, see 7. "#, is to be considered a preventive safety measure only. .he delivery capacity of inert gas generators etc is far below the requirements for active fire fighting. $ T(/IC(L(01., SA&E 'RACTICES () 2(AR3, 'ERS()AL 'R(TECTI()

.o ensure safety on board one must adhere to the following points/ 6nowledge, training and strict routine. 6nowledge of the cargo to be loaded, knowledge of your ship and her equipmentE training in the use of safety equipment on boardE strict routines in cargo handling, tank cleaning, strict routine in command and reporting, strict routine in using protective clothing etc. $.01 'oisoning an ot,er ris" 4it, #argo #onta#t

ifferent chemicals affect the human body in many different ways. .he sub1ect is comprehensive and a deeper insight in to this is beyond the scope of this book. + general information and some practical advice will be given, however. Reference is given to +ppendix,D, being an extract of 5Medical first aid guide for use in accidents involving dangerous goods5 published by ,M$', F=' and ,0' ref %7;&. .he definition of 5poisonous5 and classification of poisons is not uniform throughout the world. Fe can define a poison as a substance which is harmful to human beings %or environment&. ,n the ,M$' $ode ref %4#& a substance is classified as a poison if there is a risk of death or serious bodily harm after oral intake, inhalation or skin contact. .he 5poisonousness5 of a substance is usually expressed in terms of 0 #"3 values, 0ethal ose %sometimes 0$ #"G 0ethal $oncentration&. .hese values are determined by tests with animals and give the dose, expressed in mgAkg body weight, which kills #" < of the animals in a test series. .his figure gives a rough indication of the degree of toxity of a substance. >arious species of animals have different sensitivity, which gives some problems in applying the results to human beings. Hxamples of 0 #" values %pesticides of three categories&/ $lass 0 #" Substance * *4# mgA kg body weight paration %pesticide& 4 *4#3*#"" 3 AA3 malation 3 AA 3 7 *#""34""" 3 AA 3 bromofos 3 AA 3 ,n industry the effect of long time exposure of low concentra tion to a substance is of prime concern. .he expression used is .0> %.*hreshold 0imit >alue&, previously called M+$ %Max +llowable $oncentration&. .he .0>3value expresses the concentration of a substance in air, in ppm %parts per 7 million& or mgAcm , which must not be exceeded if a daily 93hour exposure over a long period of time shall be harmless. .0>3values are published by 8ational +uthorities and various organizations. .he most recognized list of .0>3values is probably the one published by +$-= %+merican $onference of -overnmental =ygienists ref %*#&. .he ,$S3-uide ref%*& also gives .0>3values. .he gas concentration can be measured by means of a portable apparatus described in 7. *" % rager, +uer&. .he scale of reference for gas exposure on board is normally .0> 3values. =uman beings can, however, tolerate a significantly higher concentration in a short time exposure/ Substance anger of serious poisoning after less than one hour inhalation *"" ppm 4#" pprn 4""" ppm 4""" ppm *"""" ppm .0> %Swedish *GD9&

+crylonitrile .richlorethylene $arbontetrachloride Methanol Benzene

4 ppm 4" ppm 4 ppm 4""ppm # ppm

+ person who is tired or ill is more sensitive than others and should not be asked to work with cargo handling. ,t is a good safety practice to use a breathing apparatus whenever the .0>3value in the atmosphere is exceeded

'oisoning .he poison may enter the human body orally, by inhalation, or by skin contact. +fter being absorbed by the body it may affect certain organs or give a general poisonous effect. 0ately the cancerogene effects of some industrial chemicals have been noticed. .his has led to significant reductions of hereto accepted .0>3 values in many countries. $ertain 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&. 'ther substances may be absorbed by contact to the skin without local effects %e g nitrobenzene, aniline&. -ases, in themselves non3poisonous, may be dangerous by their displacement of air %e g nitrogen as an inert gas in cargo tanks&. .he effect of a substance also depends on the temperature, its solubility in water or %skin& fat, its volatility etc. $hlorinated hydrocarbons %e g tetrachloride and chloroform& may cause damage to kidneys and liver after prolonged exposures. Symptoms of poisoning may appear many hours after contact with the substance. .ypical examples are poisoning from nitrous gases, see 7/"#, and methanol % oral intake&. .he reason for the delay being that the decomposition products rather than the original product are toxic. $ommon symptoms of poisoning are/ nausea, headache, dizziness, difficult breathing, unconsciousness. .he human body often reacts very differently to acute and chronical poisoning. %+cute poisoning 3 one contact with the poison, usually high dose or strong concentration. $hronical poisoning 3 small doses or low concentrations over a long time&. H g benzene causes reduced conscoiusness in acute poisoning but causes blood and bone marrow damage in chronical poisoning. $ertain chemicals may cause sensitizing upon first contact. 0ater contacts with the same chemical, even at lower concentrations, may cause much stronger poisonous effects. .ypical in this respect are isocyanates % e g toluene diisocyanates& where astmathic 3affects on sensitized persons may occur below .0>3 value. $.02 &irst ai

+ll cases of poisoning, regardless of which kind of poison, require certain basic common methods of treatment. +dditionally, a few particular cases of poisonous substances may require antidotes. See +ppendix D for detailed information on first aid for the various products? +fter a severe acute case of poisoning involving unconscious ness/ Bring the patient as soon as possible out into the fresh air. Rescue personnel must not take undue risks themselves, don:t therefore rush down into tanks or pumprooms where vapour may be present 3 .oo many fatalities have occurred with people who have not realised that a breathing apparatus was needed. (irst, keep the breathing passages free %prevent the tongue from falling back&. +n unconscious person should be laid on his side, face down, with one arm and one leg bent to prevent him from rolling over. 0oosen the clothes around the neck and waist and remove false teeth, see fig 7G.

Mouth to mouth artificial breathing may be necessary %avoid mouth to mouth contact with severely poisoned or contaminated patients as the rescuer may then be at risk&. =eart massage may be necessary. See +ppendix D for detailed advice. ,f the patient:s condition does not apparently involve immediate risk for his life the following measures are applicable/ +fter inhalation/ .he patient to be brought into fresh air with as little effort and strain to himself as possible, @ndue strain on the patient may affect him adversely later. Hven if the patient is free of all symptoms he should be kept quiet and rest as some gases have delayed effects %nitrogen oxides in combustion inert gas, nitrous gases&. 6eep the patient in a comfortable inclined sitting position %if unconsciousness does not prevent it&. +fter splash in the eyes/ ,mmediately wash the eyes in gently flowing water, in a washbasin, in a 1ug or a special plastic eye bath with a bottle of water, see fig !". .he eyelids may have to be forced open and the patient told to move the eyes in order that all parts will be thoroughly rinsed out. Fashing out the eyes may be very painful and pain3relief eye drops can be used. $ontinue to wash for another *"3*# minutes. ,n case of acids or alkalies %caustic& the washing must be repeated for a couple of minutes every *#37" min for the next !3# hours, preferably with a 8a$l %table& salt solution %", D 3 ", G <&. + sterilising eye ointment should be applied several times during the day. ,n case of acids and alkalies/ obtain medical advice?

+fter skin contact/ Regardless of product the area should be rinsed liberally with water, clean sea water can be used.Soiled clothes, rings, watches, shoes etc must be taken off. Fash the area thoroughly with soap and water. +lso products which do not disolve in water will be partly removed by washing in soapwater. %2oison dissolved in the skin fat will then be washed off&.

+fter swallowing/ ,f the patient is unaffected give him a couple of glasses of liquid to drink for dilution of the poison, preferably water %never any alcoholic drink&. +fter intake of alkalies %caustic& a drink of lemon 1uice can be given, or a * :D; solution of acetic acid. ,f available give medicine coal which absorbes a number of poisons and which in itself is harmless %7"3;" crushed coal tablets or coal granulate in some water&. Make the patient vomit, 8'., however, in the case of corroding %acids or caustic& products or oil products like kerosenes, gasoline, 1et fuels, when vomiting may be life3threatening. ilution of the stomach contents, however, is important. ,n case of doubt/ do not cause the patient to vomit. >omiting can be caused by giving warm salt water %one table spoon of salt to one glass of water&. .hen by putting two fingers down the throat and moving them about gently vomiting usually follows. .he procedure is described in ref %7;&. +fter certain products antidotes should be given, see advice in ref %*& and %7;&. .he most likely cargo for which an antidote may have to be used is acrylonitrile %5+85& and acetone cyanohydrine. .he remedy then is to douse some clean rag with an ampoule of amyl nitrite from the medicine kit and hold it under the patient:s nose # times with *# s interval. 'xygen should be administered in cases of weak breathing. ,t is an ,M$' $ode ref %4#& requirement to have oxygen resuscitation equipment on board. ,n cases of poisoning medical advice should be sought as soon as possible, e.g through the various radiomedical5 services. Fhile at sea also contact the shipper, who usually possesses a good knowledge of the product and its after effects. $.03 Cargo in.ormation to s,ip5s personnel

.he following advice is more or less obvious but is listed for the sake of completing the above information. ,t is a clear responsibility for the 'wner, the master and the officers to inform their personnel about the cargoes to be carried, safety procedures etc and to arrange for the proper training.

,nformation should be given partly in the form of written notices combined with informal meetings with the entire crew present when new cargoes are to be loaded or when unexperienced personnel are to be signed on. +mong other things the following information should be given/ 3 $argoes to be loadedE their characteristics as regards handling, pumping, toxity, corrosiveness, first aid etc 3 the cargo loading plan to be posted in places where it will be clearly seen by everyone on board and at the accomodation ladder, when in port. 3 2ost cargo information cards for products to be loaded or are contained on board. 'ne suitable type of card can be found in ref %i&, with examples in fig !7. +lso ref %!& and %#& show suitable information. (or 5new5 products ask the shipper for safety brochures and leaflets. See also ref %7&, %*4&, %*7&, %*;&, %*D& and %49&. 3 the personal safety equipment to be used by those involved in cargo handling, pumping, sampling etc. C6EMICALS 7 1(8R SA&ET1 () 2(AR39 Make sure that you/ 3 use goggles, gloves, oilskin or apron and rubber boots when operating cargo gear. 3 use more extensive personal protection when needed or when ordered to do so. See separate instructions for various products. 3 know what products are carried on board and that you are familiar with their respective safety measures. Study safety instructions and ask the $hief 'fficer? 3 know where eye flushing bottles are located %pump3rooms and on deck midships&. 3 now and practise how to flush your eyes with water ,MMH ,+.H0L in case of accident. Hyelids may have t; be forced open to permit proper flushing? 3 know where safety showers and water rinsing hoses are located, in pumprooms and on deck. 3 use breathing apparatus in tanksApumprooms which have not been declared safe or when ordered by officer on duty. Breathing apparatus shall be available for immediate use on deck when loadingAdischarging. 3 never enter dangerous compartments unless ordered by officer on duty. 2roper personal protection should be used and personnel should stand by. 3 know where the oxygen resuscitation apparatus is located. 3 take part in the monthly safety drills. (ig !4 Hxamaple of a safety poster 3 =ave available on board litterature on chemical cargoes, medical advice etc,

3 ,nform in particular if the cargo to be loaded has an odour threshold which is higher than the .0>3value, see ;. 'f, and that danger cannot always be sensed in advance % e g allyl alcohol, carbon tetra chloride, etylene dichloride&. 3 -ive information that most vapours are heavier than air and have a tendency to accumulate in low spaces. .herefore work below gratings in pump rooms, cofferdams, pipe tunnels etc is extra dangerous. 3 8ever take work clothes into your cabin? Soiled clothes must be washed before being used again or in the case of toxic products, destroyed. 3 Fash your hands before meals? 3 -ive information about fire fighting methods for each type of cargo on board. 3 -ive information if the cargo is water3reactive or reactive to other cargoes on board. -ive information on segregation required. 3 (or some very toxic cargoes mouth to mouth artificial breathing might be dangerous to the rescuer %e g acrylonitrile, acetone cyanohydrine&. 3 ,nformation must be given particularly if the cargo danger lies primarily in vapour inhalation %e g acrylonitrile, trichlorethylene& or skin contact %e g phenol, caustic soda, sulphuric acid&.

3 State where eye washing bottles are located %deck office, at cargo manifolds on deck, in pump rooms, on fore deck etc&. 3 ,nsist on that nobody should work with cargo gear without anyone standing by. =ave people report when going to and returning from pump rooms?

3 -ive information if any cargo is so toxic that an escape breathing mask must be used in an emergency.

$.04

S,ip in.ormation to s,ip5s personnel

,t is essential on chemical tankers that everyone knows his ship:s safety precautions thoroughly. +lso the masterAchief officer must assume responsibility for this. 8ewly signed on members of the crew should be informed about the following items and be shown around the ship to get detailed knowledge/ 3 -et to know pump rooms, cofferdams, pipe tunnels, emergency exits. 3 .he manouvering and emergency stops for cargo pumps and cargo valves. 3 Bilging of pump rooms. 3 2ump room ventilation incl information on necessary pre3ventilation before entry and emergency stop of fans in case of fire. 3 Safety showers3%in pump rooms, fore and aft on deck&, 3 -as warning equipment incl the sounding of alarms %fixed and portable&. 3 0ifting gear incl stretcher to get an unconscious person out of a 2ump room. 3 $argo tank vapour vents, incl opening, prior to cargo fillingAdischarge. 3 $argo sounding equipment. 3 0ocation of fire fighting equipment incl detailed instructions for operating them. 3 2ortable fire %powder& extinguishers placed at hose manifold. 3 Fater hoses to be connected amidships ready for washing off cargo spills %if considered proper under the circumstances& 3 $argo tank arrangement. 3 $argo piping system incl means of segregation. ,n fig !4 a set of safety instructions for a particular vessel are shown as an example. Make one which suits your ship? (or the sake of record it may be noted in the deck log when cargoAship information has been given. $.0! Sa.e pra#ti#es 4,en ,an ling #argo

Most of the items listed below have been briefly mentioned in the previous text. .he list can be used, however, as a check list for some general practices and common safety routines/ Before loading Aunloading/ 3 =ave cargo tanks to be loaded well ventilated and checked for any toxic vapours so that tank inspection can commence without any danger or undue delay. 3 2ortable %dry powder& fire extinguishers to be placed on deck ready for use. .ake off covers etc and make other fire fighting equipment on deck ready. 3 $heck cargo hoses to see that they have not deteriorated, that flange connections are intact, that there is an electrical bond between hose flanges and that the working pressure for the hose is marked on it. ,f there is any doubt about the hose:s condition, find out when the hose was last pressure tested, see 7. "4. +fter connection of the hose to the ship:s manifold the. flange should be pressure tested for tightness with air at ;3*"kpAcm 4 %shore valve closed&. Fith corrosive and toxic cargoes a protective cover should be placed over3the hose flange connection. + drip pan should also be there. 3 Hstablish communication routines with the terminal operators regarding flow rates, emergency stops, topping up,

general alarm etc. 3 6eep unauthorized people away from the cargo deck and hoses. $heck that vapour releaseAadmittance to the cargo tanks is unobstructed %2A> valves moveable, lids opened, flame screens unclogged etc&. 3 6eep hatch lids closed except when taking ullages, sampling etc. 3 See to it that everyone engaged in cargo handling is wearing the correct protective clothing %depending on whether there is danger to the skin on contact or inhalation of vapour. 3 +void getting the blast of vapour in your face when taking ullages during loading. o not stand 5upwind5 or 5downwind5 of an ullage hole but stand beside it with the wind across your face. 3 6eep pump rooms ventilated with fans running during cargo transfers. 3 6eep moderate loading rate during the first phase of cargo transfer to an empty tank %not necessary with inerted tanks&, particularly with petroleum products of the type kerosene, 1et fuel. .he liquid velocity should be kept well below , mAs in the cargo piping until the liquid covers bottom framing or about ", # m above bottom. %Risk for static electric charges and incendive sparks. See ref %G&&. * mAs means for a !N pipe 3 AA 3 3 AA 3 9N 3 AA 3 3 AA 3 3 AA 3 *4N 3 AA 3 7" m.7Ah **! 3 AA 3 4#9 3 AA 3

3 .he final ullages should not be taken before 7" min after loading is finished if conductive tape is used %when possible static electric charges are likely to have been dissipated&. 8on3conductive tapes to be preferred. 3 8ever go down into a pump room without reporting to someone on duty when leaving and on returning. 3 8ever work alone in confined spaces? 3 =ave breathing apparatuses on deck ready and available when handling toxic cargoes. 3 Remember that an explosimeter only indicates the risk for explosive conditions 3 toxic conditions may arise at far lower concentrations than detectable by an explosimeter instrument. @se also a toxiometer for health readings. See 7.*" and ;."*. 3 8ever wash and steam a tank simultaneously. Many explosions have proved this to be a dangerous combination, electric charges are a likely reason. ,t might be dangerous to enter a tank containing oxidizing vegetable oils %e g castor seed oil, cotton seed oil, ground nut oil, linseed oil& during the last phases of discharge. .here are indications that conditions with lack of oxygen in the tank atmosphere may develop. @se a breathing mask with fresh air supply or forced ventilation. 'ne 5half3mask5 and one emergency mouthpiece with nose clamp is shown in fig !9. .he maker will be able to advice on types of filters for the cargoes in question. (or escape purposes a better equipment is handy air bottles with masks for short time use. 3 +ir compressor for recharging of breathing air bottles %4""37"" atm& should be standard equipment on chemical tankers. Below is listed suitable equipment for operational personnel for various typical cargoes and operations on board/

a& 2roducts involving little or no danger upon skin contact, moderate vapour toxity and relatively high volatility %low boiling point& as e g/ petroleum products, petroleum naphta, toluene, benzene, xylenes, methanol, acetone, methyl ethyl ketone, gasoline, styrene, @se/ Rubber boots, gloves. =ave in your pocket for use / %when taking ullages, sampling etc& 2lastic goggles + breathing apparatus %compressed air type 4"" atm& should be kept ready for immediate use if sudden entry into a gas3filled pum3proom should become necessary. Hye washing bott les available on deck and in pump rooms. Hxplosimeter and toximeter available. b& 2roducts with a strong corrosive effect on human tissue, moderate or low vapour toxity as/ sulphuric acid, caustic soda, phosphoric acid %eye danger primarily&, acetic acid. @se / -oggles or face shield, oilskin or apron, rubber boots %trousers outside&, long cuffed rubber gloves, helmet. Hye washing bottles available on deck and in pump rooms c& 2roducts which involve great danger upon skin contact %poisoning& and high vapour toxity as e g/ phenol, acrylonitrile, acetone cyanohydrine, allyl alcohol, aniline, chlorosulfonic acid. @se on open deck %as a minimum&/ skintight fitting goggles or face shield, oilskin, rubber boots %trousers outside&, long cuffed rubber gloves %tucked inside 1acket sleeves&, helmet. =ave in your pocket for immediate use/ -as mask %full mask or emergency mouthpiece with nose clamp&. Hye washing bottles available on deck and in pump room . +t least two breathing apparatuses %compressed air types& should be kept available on deck for immediate use. .oximeters available on deck. Fhen handling hoses or entering contaminated areas/ use full protective suit, preferably of pressurized type with hood and permanently attached rubber boots. .he ,M$' Bulk $hemicals $ode ref %4#& gives some general information on the amount of and the type of personal protecti;n to be provided on board. (or the purpose of being a check list is given below what might be considered the minimum amount of equipment on board a chemical tanker of 7" """ tdw. ,ndicated, in brackets, is the ,M$'3$ode minimum requirement %where given&. +n 5x5 means 5sufficient5/ 8umber of ; fighting %7& Breathing apparatus, compressed air type, with air bottles % in addition to S'0+S fire equipment& min. 4" minutes action time. Compressor with fittings etc. for charging of air bottles for breathing masks. +ir bottles to above %D l at 4"" atm or ! * at 7"" atm&, as reserves. Breathing hood with filters and 4 x 7" m hose. 2rotective suit, chemical resistant, overpressure type with hose connection. Rubber

* *4 7 7 %7& boots attached

with chemicals resistance list. ; %7& 2rotective suit, chemical resistant, rubber boots %attached with chemicals resistance list& 7" 4"p *" 7" p #" p *" p 7 *4 %x& M'ilskinN, chemical resistant. %7& %7& %7& %7& %7& %7& %7& 0ong rubber boots. +pron -loves, long, sleeved. -oggles, plastic, tight fitting. (ace shields. Steel cored rescue line with belt and hook. Safety lamp.

4 %4& -as indicator for flammable gases %double scale&, with calibration unit. 4 %4& 'xygen indicator. 4 %4& -as indicator for toxic vapours %with liberal supply of detection ampoules for likely cargoes&. *" %x& Hye washing bottles. * %*& 'xygen resuscitation equipment. %all on %all on -as mask for emergency use, with filters for cargo vapours %if very toxic and volatile cargoes are to be board& board& carried&. %x& %i& %x& %x& %x& %*& %x& %x& +ntidotes. See ;."4 and ref %7;& re cargoes. Stretcher suitable for use in pump rooms etc %Japanese type& Shower %on deck and in pump rooms& $argo and medical information %e.g ref %*&, %4&, %!&, %#&, %*;&, %*D&, %44&, %4#&, %7;&&.

8B/ 8itrile rubber %gloves& is not resistant to acrylonitrile and should not be used with this product. : TA); CLEA)I)0

$leaning of tanks is usually the responsibilty of the ship. See paragraphs 9 and G in 5B,M$=HM>'L5 in +ppendix 9. .ank 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. Hxamples/ glycol intended for cosmetics or pharmaceutical purposes requires cleaner and completely odourless tanks than does glycol intended for antifreezesE caustic soda for making paper is more sensitive to iron contamination than caustic soda for the aluminium industry. ,t must be mentioned first that the ma1ority of cleaning op 3rations on board chemical tankers are being carried out by means of water washing only. (urther chemical cleaning is required for only a limited number of cargoes, but these cases may be very important. 'ne must take into consideration the nature of the previous cargo and the cargo to be loaded, time factor, available equipment and cleaning chemicals etc. ,n +ppendix # it is stated the necessary degree of cleanliness for a number of products, in line with what cargo surveyors normally require. -enerally speaking one should use mechanical tank cleaning methods, that is usually washing with water, before applying more expensive methods involving chemical cleaning agents. .he most expensive, and least safe, method is manual cleaning, which should be kept to a minimum. Manual work should preferably be reduced to inspection and possibly to a final drying up of washing water only. ,t is important to drain the tanks as much as possible in order to deliver all cargo and to reduce pollution of the seas to an absolute minimum. .his will now be even more important with the anti3pollution $onvention of *GD7 %see *"."*&. Hxamples on measures on how to obtain the best possible cargo stripping/ 3 ue regard to ship:s trim and heel. 3 >iscous cargoes may first be stripped from the various tanks to one tank near the pump room and from there be pumped ashore. 3 6eep the cargo temperature sufficiently high so that the cargo drains also from remote corners of the tanks,

especially in cold climates. 3 Faxy deposits under the heating coils can sometimes be melted out be means of filling with water and then applying heat to the coils. 3 Sometimes steaming is allowed during discharge of molasses, which facilitates draining of molasses from the bulkheads. 3 >egetable oil tanks may in the last phase of discharge be recirculated and hosed down with vegetable oil taken from the cargo pump delivery side %see warning under ;. "#&. Similarly phosphoric acid can be recirculated to loosen sediments on the tank bottom. 3 rain cargo piping to shore. ,t is useful to have a small stripping pump with #" mm delivery line to the hose connection for delivery of contents in the cargo piping to shore. 3 Before loading sensitive cargoes/ mudboxes, valve bodies and pump housings must be drained by opening the drain plugs %with due regard to personal safety&. .he following text is intended as a general guide and will give some practical examples on problems and methods. Reference is given to 5.ank cleaning -uide5, ref %*"&, excerpts of which are given in +ppendix !. See also ref %**&. .he information given should not substitute your own or others: good and proven methods? +lso consult shippers and tank inspectors coming on board. +nalyze the properties of the previous cargo and take advantage of its 5weak points5, e.g as follows/ 3 Fater solubleK ,f the cargo is reasonably soluble in water then chemical cleaning agents are unnecessary in most cases. 3 Fill an increased cleaning temperature cause a beneficial reduction of cargo viscosity and lower surface tension or could it cause the opposite/ that cargo residues polymerize or oxidize %5dry5&. 2olymerization and drying must be avoided, therefore the first cleaning operation must be carried out cold. 3 ,s it possible to emulgate the cargo in water or in water with emulgators addedK Make a test on board. 3 Fill the product be affected by alkaliesK $austic soda is a relatively cheap and easily available alkaline chemical. 3 Fill the product dissolve in other easily available products by which the tank walls can be treatedK %Succesively 5upgrading5 or 5floatation5 methods&. 3 Fill cargo residues vaporize without leaving any tracesK 3 $an cargo remains be safely mixed with the cargo to be loadedK ,n many cases it is not known what the next cargo will be but sometimes this method can be applied. :. 01 're7 #leaning < 4as,ing= 2ractically all cases of tank cleaning start by washing with water. .his is mechanical removal of cargo residues. .his method has a slight emulgating effect %forming minute droplets of cargo suspended in the washing water&. .he water pressure should preferably be *4 3 *! kp cm 4 with a capacity corresponding to ! washing machines %9"3*"o m 7 Ah&. .he washing water heater should have a capacity of yielding 9" degr. $ washing water with 4 3 7 washing machines working.

Fhile washing one should simultaneously drain the tank at the same rate in order to assist the cargo residues in their flow towards the tank suctions. ,f not, the residues will have a3tendency to come to rest anywhere on the tank bottom. a& 2roducts with good solubility in water %data on solubility in ref %*&, %7&, %#&, %*;&/ 2re3cleaning can normally be carried out with cold water. Hxamples are/ mineral acids %sulphuric acid, phosphoric acid&, alkalies %caustic soda, ammoniaApotash solutions&, alcohols %ethanol, methanol, butanol&, acetone. .he more viscous water3soluble products may have to be pre3cleaned with hot water, examples/ glycols, glycerine, molasses. 8ote/ sulphuric acid must be washed with copious amounts of water to guarantee rapid dilution and reduce risk of heavy corrosion. b& 2roducts which are volatile and vaporise without any traces frequently need no tank washin , only ventilation and possibly steaming of the tank. Hxamples/ acetone, methyl ethyl ketone, hexane, methanol, butanol, propanol, toluol, trichlor ethylene. ,f water flushing is not carried out/ remember to drain all cargo lines, pumps etc. raining out cargo may be a difficult process to carry out safely and therefore water flushing and subsequent draining of the piping may be an advantage. .hereafter draining of water from the piping system can be carried out. c& Some vegetable oils and animal oils %fatty acids& oxidize and 5dry5 upon application3 of air and heat. Hxamples are/ castorseed oil, cottonseed oil, groundnut oil, linseed oil, spermoil, talloil. 2re3cleaning must then be carried out with cold water. 'therwise the residues will dry up and harden and may be very difficult to remove. (inal washing, however, can be carried out hot, see D. "4. d& >egetable oils and animal oils of non 3drying type should preferably be pre3washed directly with hot water %9""$&. Hxamples/ coconut oil, palmkernel oil, palm oil, tallow, whale oil. e& 2olymerizing products should be. pre3washed with cold water or the tanks should be flooded with water. =ot water may cause deposits of polymerized material, sometimes very difficult to remove. Hxamples on such products/ styrene monomer, vinyl acetate, acrylonitrile, vinyl chloride. f& =eavy oils, lubrication oils, lubrication oil additives, gas oil are normally pre3washed with hot seawater %9""$& although cold water can also be used. g& %$rude oil is mentioned as a reference. $rude oil with a relatively high percentage of light fractions such as +rabian crudes are often pre3washed cold and then hot. ,f hot water is used the light fractions are liberated first and then the residue tends to be tougher and more difficult to remove. =eavy crudes, however, e.g Boscan crude with little or light fractions can be washed directly with hot water. & :.02 &inal #leaning Method of cleaning to be used depends on both previous cargo and cargo to be loaded. $heck with +ppendix ! and # regarding cleanliness requirements for cargo to be loaded. +s a general rule the tanks and piping shall be completely drained of water or residues before loading. .he bottom of the tanks may have to be dried up with rags. Some cargoes are very sensitive to chloride contamination. .he tanks to be loaded with these products have to be washed out thoroughly with fresh water. Hxamples on such products are first of all glycols and alcohols %methanol& but also aromatics and acetates. >egetable and animal oils, gasoline, heavier oils, caustic soda do not normally require a fresh water rinse of the tanks to be loaded. ,a& 2roducts with good solubility in water/ .he final cleaning is a direct continuation of the pre3cleaning with water, possibly with hot water for viscous products. ,f sensitive cargoes are to be loaded any odours that remain must be ventilated andAor steamed away. b& >olatile products , as mentioned above, do not often require cleaning after discharge. c& and d& >egetable 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. .he oil residues will then be converted into soap, which is a water soluble product and which will be rinsed off the bulkheads. .he cleaning chemical is consumed quite rapidly if there are un necessary amounts of cargo left. +bout *"" kgs of

caustic soda are required, counted as a #" < solution, to saponify #" kgs of oil. @sually the cleaning chemical is added to the washing water in a 437 < concentration of caustic soda %max # <. Farning/ alkaline washing solutions are dangerous to eyes, use goggles? ,M2'R.+8./ Iinc silicate tank coatings are adversively affected by alkaline cleaning chemicals. 8e ver use caustic soda or alkaline cleaning agents in zinc sili cate coated tanks ? Mineral oils and waxes cannot be saponified. ,t is possible to remove vegetable and animal oil residues by the use of detergent cleaning chemicals. etergents reduce the surface tension of the washing water, thus 5lifting off5 the residues. $leaning 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& 2olymerizing 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& =eavy 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. +fter the pre3wash/ hot washing with cleaning chemicals of a detergent type, solvent cleaner, emulsifier or synthetic soap. Hmulsifiers assist in forming minute droplets of the product suspended in the water. .he 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. + dosage of *34< to the washing water is usually recommended. $ertain emulsifiers are so effective that the emulsion will not break up %water and product separate& after a long time, even if heated. ,f such a washing solution is to be discharged to a slop3receiving facility ashore difficulties may arise. $heck with the supplier of the cleaning chemical and the slop3receiver before making your purchase of cleaning chemicals? 5Solvent cleaners5 contain water3soluble 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. etergents contain wetting agents %tensides& which reduce the surface tension of the water, thus 5lifting off5 impurities from the tank wall. Fhen several cleaning chemicals are used their sequence of application should be/ %water&, detergentAalkaline %caustic&, synthetic soap, emulsifier, solvent cleaner, solvent. 0eaded gasoline leaves posionous lead compounds on the tank walls which is unacceptable if edible products are to be loaded next. ,n +ppendix ! a method is described where the tank is washed with *" < acetic acid to remove lead remains. .his method does not, however, guarantee that the tank will pass a chemist:s test and be accepted for edible products. Fine has a particular tendency to absorb lead compounds from the tank walls. Hdible products should not be carried until after several other intermediate cargoes. ,t is becoming more and more common to apply the cleaning chemical in undiluted form, see D. "!7. :. 03 ( our

Some products are very sensitive to foreign odours, usually stemming from previous cargoes in the same tank. Hxamples of sensitive cargoes are/ glycols, glycerine, vegetable and animal oils, molasses. 'dours remaining after a thorough tank cleaning are usually best removed by steaming andAor ventilation of the tank. Steaming 5sweats out5 cargo from pores etc. $argo piping may also have to be steamed out. Hpoxy coatings should not be heated above ;" 3 %9"& degr.$, zinc silicates tolerate somewhat higher temperatures. So called deodorant fresh air sprays have an effect only on the atmosphere in the tank. @sually the odours stem from cargo residues on the actual tank walls and will

therefore soon come back. .he spray method is more of a symbolic value with regard to the care of the cargo. :.04 'ra#ti#al #leaning met,o s e ire#tly to t,e 4as,ing 4ater.

:.041 Cleaning agent a

.he cleaning chemical is in1ected into the washing water by means of a dosage pump, usually air3driven, through a fitting attached to the washing pipe on deck. Sometimes the cleaning chemical is added to the suction side of the washing water pump, thus eliminating the need for a dosage pump. But the dosage becomes less accurate and the method is more cumbersome in the latter case. + direct addition of cleaning chemical to the washing water is quite common, but chemical consumption tends to be high and its full cleaning effect is not always utilised. *34 hours of washing is usually to be recommended. .he final rinsing being sea or fresh water, depending on the product to be loaded. :.042 Re#ir#ulation o. t,e 4as,ing 4ater -ives a better utilisation of the cleaning chemical. + mixture of # 3 #" tons of hot water with the recommended amount of cleaning chemical is made in a cargo tank, a slop tank, a cofferdam or a special tank for the purpose. .he water may be further heated by means of heating coils. + cargo pump may serve as a washing pump with delivery to the washing line on deck, and then to the washing machines. +nother cargo pump or stripping pump drains the water back to the containment tank where the cargo residues can be removed by carefully drawing out the washing water from the bottom. Fashing should only be carried out on condition that the tank atmosphere is well below 0H0 %lower explosive limit&. $heck during washing? Fashing should be carried out under inert gas atmosphere if cargo vapour concentration is above 0H0. .here are indications that contaminated washing water may cause incendive static electricity sparks. .his refers in particular to recirculation washing. .he recirculation method can be used with all types of cleaning chemicals. 'ne advantage is that one can easily incorporate ma1or parts of the piping system in the cleaning circuit. Remember cross3overs and risers to deck? (inally rinsing with sea or fresh water. :.043 T,e #leaning #,emi#al #an %e applie un ilute ire#tly onto t,e tan" 4alls. .his method is becoming quite common. .he cleaning chemical is sprayed directly onto the tank bulkheads by means of a high3pressure %portable& pump and a long lance, which the operator can direct all round the tank. .he operator must use protective oilskins, goggles and preferably a breathing mask too. .he cleaning chemical is left on the tank walls for 4" 3 !" minutes. .he tank is then washed by hot water. .he process is repeated where necessary until the tank is clean. .his method is very effective. ,n a similar operation the cleaning chemical is added to an e1ector, which draws it into the steam when steaming the tank. .he tank should first have been steamed thoroughly. +fter steaming with a cleaning chemical, steaming is continued for a while. (inally rinsing with sea or fresh water. Remember to keep the hatch lid slightly open to eliminate excess pressure during steaming or sub3pressure after steaming is finished? :.043 A .loatation met,o is sometimes use (or the final cleaning to achieve a high degree of cleanliness after heavier hydrocarbons such as lubrication oils, lubrication oil additives and before loading hydrocarbon3 sensitive products such as methanol. %8ormally a tank is 5upgraded5 to methanol standard via two3three intermediate cargoes of aromatics &. .he floatation method should only be used after first washing with cleaning chemicals. .he

method is then very effective, but it is less effective if cargo residues on the tank walls are of any appreciable thickness. .he tank is first filled to a level of ", ! 3 ", 9 m from the bottom with a strong non water3soluble solvent, which is also reasonably cheap. .oluene is usually used. .hen the tank is slowly filled with water, thereby lifting the toluene on top of it. +fter filling, the water is slowly drained again until the tank is empty. .he top layer of toluene is then transferred to the next tank and the process repeated %with the same water used again to minimize solvent losses&. .he filling and draining can be done with a level change of, say ", # 3 4, " mAh depending on the degree of contaminants on the tank walls. .here have been advanced warnings that this floatation method, although frequently used, might involve hazards as regards static electricity charges in the interface between the two liquids. ,t is wise to pump slowly in order not to exceed , mAs in the filling pipe, see also ;. "#. .he process should preferably be carried out with the tank inerted, see 7. "#. :.04! Steaming 4it, a sol>ent $an also be done as a final cleaning process, after washing with a cleaning chemical. .he method will only be effective for removal of the very last traces of a previous cargo. (ill the tank with water to 1ust above the heating coils and add a non water3soluble solvent, usually toluene or xylene. .he water is then heated by means of the heating coils and the solvent vaporises. .he solvent condenses to a certain extent on the tank walls and dissolves minute amounts of cargo residues, which after draining of the tank can be washed off using water withAwithout cleaning agents added. .he amount of solvent should be of such small quantities that the forming of explosive mixtures in the tank is avoided. $hoosing 4A7 of 0H0 as a guide one arrives at the following maximum amounts of toluene/ .ank size 4"" m 7 abt *" l of toluen #"" m 7 3AA3 4# 3AA3 *""" m 7 3AA3 #" 3AA3 (or other solvents the corresponding amounts can be calculated based on the fact that one grammolecule %Oas many grams as the molecular weight& occupies 44,4 litres of volume at normal atmospheric pressure and temperature. :.04$ Rinsing 4it, 4ater is normally t,e .inal #leaning pro#ess,

@nless the cargo remains can be completely vaporised away. Remember that certain cargoes to be loaded may require fresh water rinsing %risk for chloride contamination&, e g methanol, ethanol and glycols. Stainless steel tanks shall always be finally rinsed with fresh water, otherwise there is a risk for tank pitting corrosion, see !."4. (inally the tanks should be ventilated dry and any water left be dried up with rags prior to loading. :.0! Cleaning o. stainless steel Stainless steel can be cleaned with all the methods mentioned above. Regarding removal of tank wall discolourations see !. "4. * D."; Rust MdescalingN ,n the trade of chemicals loose rust will never be accepted upon loading. .he rust itself may be harmless for many products, e g gasoline, but the rust may contain residues from previous cargoes, which may contaminate the next

cargo. -as freeing may also become more difficult if large amounts of rust collect on the bottom of the tank. ,t is sometimes possible to scrape off loose layers of rust. +nother method, sometimes used but relatively expensive, is 5electrochemical descaling5. + provisional, but very strong, anodic protection system consisting of +lAMg strips is tack welded to the tank interior. .he tank is then filled with %salt& seawater for a couple of days. .he anodic alkaline process breaks off rust from the bulkheads and the rust can be washed down. 5'nly5 rust3removal remains. .his method is intended for uncoated tanks only.

TESTI)0 (& TA);S A)3 CAR0(ES

.he following pages describe and discuss some of the most common tests and checks that are made on oil and chemical cargoes including testing tank walls for cleanliness. .esting 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. ,f possible one of the ship:s deck officers should take part in the cargo sampling, cargo testing, tank cleanliness examination etc. =e should make notes and observations on the work of the surveyor with a view of protecting his party:s interests. ,t is therefore necessary to have a general knowledge of the various procedures, without necessarily being able to carry them out himself. ,n the following text, how3 ever, there will be3mentioned tests which are easily carried out by the ship:s staff by relatively simple means. + small laboratory with a stainless steel sink, a rack for *" 3 4" bottles of chemical reagents, test tubes %8essler tubes& and a supply of distilled water are an advantage to have on board. ,n some remote ports independent surveyors may not be available. .his gives the chief officer added responsibility in following the shipper:s or receiver:s instructions, particularly if he is requested to sign their protocols etc. escribed below are a number of tests, which are commonly used by surveyors. Most of the tests are of a physical nature and are relatively easy to carry out on board. 8ormally the test results do not give any exact answers as to contaminations etc but have to be 1udged in relation to commonly accepted standards in industry or agreed values between the parties. (urthermore, the answers are often only indices of contaminations. ,n case of any disagreement full laboratory examinations may have to be carried out. ,t is then of the outmost importance that the ship secures samples, sealed by an independent surveyor or by both parties, of the cargo parcel in question for further analysis. .he text below often refers to +S.M3standards %+merican Society for .esting and Materials&. .he standards are contained in a series of updated books, obtainable through good bookstores or from/ +merican Society for .esting and Materials, *G*; Race Street, 2hiladelphia, 2+ *G*"7, @S+. Similarly +2, %+merican 2etroleum ,nstitute& issues various standards, which are generally applied. +ll measurements and tests have their tolerances, usually rather widespread and with correspondingly great economic consequencies. ,t is good practice to take all readings twice, repeat important tests twice etc? Fith ships engaged in special trades it might be useful to be able to carry out the more common tests on board and to train personnel correspondingly. .his refers in particular to the testing of tank walls for cleanliness. Many delays can be avoided if the ship:s officers can satisfy themselves that the tanks are properly cleaned before entering port, using the same methods as the surveyor coming on board does. ?.01 Sampling o. #argo $argo samples are taken for the purpose of checking whether the cargo satisfies a given specification or not. Samples are also taken to establish if contamination has occurred during the voyage, during loading or unloading or prior to loading. +fter examination of the tanks, mudboxes, piping etc %as far as possible& for cleanliness it is usual to load sensitive chemicals into the ship:s tanks to a level of approximately ", 7 m and then take samples from the tanks, presuming that any previous residues in the piping are by then dissolved into the new cargo %::soak test5&. Similarly samples are taken from an initial discharge into container tanks or similar located on the shore before commencing unloading at full rate to the shore storage tanks.

,f a 5soak test5 upon loading is turned down by the surveyor or the shipper and loading stopped, the chief officer should then request sealed and identified samples of the cargo lot in question, from the ship:s tanks as well as from the shore tanks. By these means the shipowner may be able to protect his interests in case of any dispute. Sometimes drip3samples are taken from the loading manifold during loading. .his method is simple, but not always fully representative. .he pumping rate may vary during the transfer, whilst the sampling rate is more or less constant. (urthermore it is difficult to guarantee the proper identity of a sample taken over a long period of time. .his is not meant to discourage the ship)s officers from taking a drip3sample during loading, but only to mention the weak points of the method. ,n fact, drip3sample during loading may be the only way to establish whether a cargo was contaminated during the pumping on board or ashore. Before unloading cargo samples are normally taken from the ship:s tanks. .he cargo samples should be sealed and marked on board, particularly if no independent surveyor is present. .he ship should keep one sample for future reference in case of any disputes arising. .he samples should be stored in a dark and cool room especially put aside for this purpose. .he room should have steel bulkheads and be open to the weather deck. Samples of products which deteriorate or change with, time %e g styrene, vegetable oils& have a limited purposeful storage time on board. Fith e g phosphoric acid the samples may remain representative as regards chemical composition, but may not be so as regards contents of sediments, =owever, normally the samples are stored one year, which is the normal respite for making any claim. Sampling at deep levels is carried out with containers which are lowered upside down or have valves or other means of filling themselves up at the deeper level. Sampling at various different levels is necessary for products which have a tendency to stratify, viz phosphoric acid which may contain a higher percentage of solids near the tank bottom than at top level.

?.02 Cargo temperature etermination .he temperature difference between the top and bottom of a tank may be considerable. .his applies particularly to shore tanks, where the ship)s officers are sometimes requested to attend when readings are being taken. +S.M standard *"9#3;# %+2, 4#!#& rules that temperature readings are to be taken at three levels when the tank depth exceeds !, # m. 'rdinary thermometers should be kept immersed at least # minutes at each level. .he most common type of thermometer is shown in fig #". +s regards skin3contact dangerous products such as phenol, acrylonitrile etc one should, if possible, avoid handling contaminated thermometers. Readings are much better taken by means of thermometers pocketed in the discharge manifold. -lycerine or other suitable contact medium should be filled in the pocket in order to give a good thermal contact. Simple, portable, remote reading thermometers which can be lowered into the tank would be a welcome development. ?.03 Spe#i.i# gra>ity, ensity Specific gravity expresses the weight of a unit volume of a matter compared with the weight of the same volume of water, both at a defined %but sometimes different& temperature. Hxpressions such as S4"A4""$ are used in the petroleum industry. .he first figure denotes the temperature of the product and the latter the temperature of the water used as a comparison. Specific gravity includes the effect of air displacement.

.he specific gravity of water varies as follows/ ! degr. $ *,"""" *# degr. $ ",GG94 4" degr. $ ",GG*7 ,f a specific gravity S- 4"A4""$ is to be converted to S- 4"A!"$ %!"$ is a common reference temperature& multiply as follows/ S- 4"A! 'ther examples/ S- *#A! S- *#A*# O S- *#A4" x ", GG*7 *,"""" O S- *#A4" x ",GG*7 ",G"94 O S- 4"A4" x ",GG*7 *,""""

.he tendency is now to use metric units in cargo calculations. .he expression specific gravity is then substituted by density and weight with mass. ensity is expressed in absolute figures, viz kgAm 7 at a defined temperature. + recalculation from specific weight to density involves a correction for the displacement in air by means of a 5vacuum factor5/ ensity O Specific gravity >acuum factor .he vacuum factor varies slightly with density %specific gravity&/ ensity *," ",G ",9 ",D >acuum factor *,""*"9 *,""*44 *,""*7G *,""*;* .he difference between density and specific gravity is, as can be seen, small. +n error in application gives a discrepancy of abt *4 m P7 for a cargo of *" """ mP 7 %at S- ", G&. ensity %and specific gravity& is measured by means of an areometer %hydrometer& or pycnometer.

.he areometer consists of a displacement body with a graduated scale, see fig #*. .he accuracy in reading gives a maximum of three correct figures, the fourth figure being doubtful. .his means an accuracy of ", *3", 4 <. .his accuracy is generally insufficient for cargo quantity determination. .he areometer is, however, well suited as an instrument for a general check of cargo density on board. See also +S.M standard *4G93;D %+2, 4#!D&. + set of areometers for density ranges ", D to *, " and *, 7 to *, 9 %alkalies and acids& should be on board. .he pycnometer consists of a small glass retort with an accurately determined volume %certified pycnometers available&. .he specific gravity is determined by weighing the pycnometer empty and filled with liquid. .he result is obtained with five correct figures which is much better than the areometer

principle. .he determination is generally made at 4" " $. .he use of pycnometers on board is not practicable due to the need for a very sensitive weight scale. Specific weightAdensity is part of all product specifications as a check on concentration, mixture etc. .he S-Adensity falls with the rising temperature. >olume correction factors are used for recalculation %per degr. $ or degr. (& or tables %for petroleum products& available from, e.g +merican 2etroleum ,ndustry %+2,&. + warning/ ,t sometimes happens that cargo density and thus the quantity is determined at both the loading end and the discharge end by means of areometers. 'bviously therefore there will be discrepancies in the two quantity determinations simply due to the relatively poor accuracy in the density readings. +s a result questions regarding cargo claims may arise. .he answer is to use the 5as loaded density5 %whether completely correct or not& and correct it for the change in temperature at the discharge end. .his McalculatedN density is then used in the quantity determination upon discharge. .hereby it can be established with good accuracy whether cargo has been lost or not. .here are also other specific gravity scales. $onversion can be carried out thus/ a& +2,3scale, commonly used for petroleum products/ +2,3gravity %at ;""(& O *!*,# 3 *7*,# S- at ;"A;"n degr. (

b& Baume3scale, used for liquids heavier than water, e g sulphuric acid/ S- O *!# %*!# Q degr.Baume&

.here is also a Baume3scale for liquids lighter than water. ?.04 Colour etermition Most products shipped in chemical tankers are pure and well defined. .he colour is known and any deviations indicate the presence of contaminants. Most chemicals, furthermore, are clear and translucent. + milky or turbid +ppearance indicates that contaminants may be present. + sample is best studied in a test tube against a black or white background in good daylight. Hmpirically a number of colour scales have been established. .hey are each particularly suited for certain kinds of products. + method called +2=+ %=azen& is often used for very light products, defined in +S.M 3*4"G, viz aromatics, ketones. .his colour scale is defined with an origin in *"" cc distilled water %value "& to succesively higher values %max #""& by adding +2=+3solution %a platinum3cobolt salt solution&. .he number of cc +2=+3solution %min # cc& added to the distilled water gives the +2=+3colour shade number. + comparison is made against a white background with a product sample in one test tube and a matching +2=+3solution in another. .his method can easily be carried out on board. +2=+3solutions are best bought from a laboratory, already premixed for a number of shades. .he Saybolt colour scale uses coloured glasses against which the sample is compared in a defined apparatus. .he colour scale goes from plus 7" %lightest& to minus *; %darkest&. .he Saybolt scale is widely used in the petroleum industry. .he method is defined in +S.M *#;3;!. .he Saybolt method requires a special apparatus, is somewhat complicated and not particularly suited for use on board ships. .he -ardner3scale uses sealed reference tubes for comparison with samples in a tube of the same diameter. %.he (+$3method resembles the -ardner method but has a different graduation&. .he -ardner scale goes from * 3 *9 and is defined in +S.M *#!!3 ;7.. .he 0ovibond3scale has several different colours %yellow, blue, red& and uses a test cell with a variable depth. .his method is used for e.g vegetable oils. +S.M *#"", previously called 82+ defines colour scale and an apparatus suitable for field work and application on board. + test sample is compared with coloured glasses in a revolving magazine . .he scale goes from i %water& to 9 %extra dark red&. .he name 582+ grade . . . . 5 is still often used in shipping when a prospected cargo is circulated or when a vessel:s cleanliness is described. + cargo may be accepted at 82+ 4, with discharge permitted at 82+ 4 *A4. + certain amount of degradation in such a case can be permitted. Fith a colorimeter on board one can take samples and by experience get an idea of how much of the previous cargo residues can be left unattended without risk for cargo claims %refers to petroleum cargoes rather than to chemical products&

?.0!

-A#i

4as,-

.his method is used to determine if petroleum hydrocarbons are present in aromatic compounds. +romatics %e.g toluene, xylene, benzene& are unaffected by sulphuric acid, but oils and most other contaminants are affected, causing a discolouration. .he method is suited for application on board and can be used as a check that proper tank cleaning has been accomplished. .he method is defined in +S.M 9!93;4.

+ test tube is filled with D cc conc %G; <& sulphuric acid, on top of which is filled 4* cc of the product sample. .he tube is then shaken !" 3 #" seconds %*#" times& and is then left to settle for a period of time. .he colour of the acid in the bottom of the tube is then compared with the standard shades where " corresponds to water and *! to a dark yellow colour. .he acid wash method is used if there is any suspicion that a cargo of aromatics may have been contaminated by a previous oil cargo. .he method is also used as a check that a tank is sufficiently cleaned before loading aromatics. + surface of about one m 4 is carefully cleaned with clean cotton and an aromatic, e g toluene, and the liquid wrung out and tested as the cargo sample mentioned above. 'ne can also take rust sediments %uncoated tanks& and dissolve any oil contaminants by means of toluene, which is then tested by this method. (inally a difficult question arises/ how much of cargo contaminants can be tolerated on the tank wallK Make tests and train your own 1udgement? ?.0$ 3issol>ing #ontaminats .rom rust +s a rough check if cargo residues hidden in rust may discolour a cargo to be loadedthe following check can be made/ Break the rust into pieces, ", # 3 *, " cm in size, and place them in a clean bottle. +dd some of the product to be loaded %or other similar available product& and leave for # min. ,f no discolouration has occurred by then, shake the bottle vigorously and leave for another *# min. ,f still no discolouration appears the tank could be cleared for loading. ,f there is a discolouration/ filter the contents through double filter papers in order to remove any possible suspended rust particles. + non3discoloured liquid after filtering should also clear the tank for loading. + discolouration means that the tank requires further cleaning. 'bserve/ this simple test does not necessarily clear a tank for loading of e g aromatics, but it may prevent you from trying. ?.0: ?.0? 6y ro#ar%ons in met,anol 7 -4ater mis#i%ility testC,lori es

Methanol is very sensitive to oil contaminants. .he following test method uses methanol as a testing medium. .he methanol must therefore be guaranteed free from any hydrocarbon contaminants. +bout one m 4 of the tank wall is carefully washed with cotton and about !" cc methanol. .he methanol is wrung out and put into a test tube. .hen ;" cc distilled water is added. .he mixture is well shaken and left to settle for 4" min. ,f the solution remains a clear liquid the tank wall can be considered to be clean, but if the solution has turned milky or only slightly milky it is an indication that the tank should be cleaned again before loading methanol or any other oil3sensitive cargo. .his method should be a standard practice to be carried out by the ship:s personnel. .he method can, of course, also be used as a check on the cargo upon loading and discharging. ?.0? C,lori es $ertain cargoes are very senstive to chloride contamination, in particular glycols, methanol, ethanol %see +ppendix #&. +s mentioned before the tanks should be finally washed with fresh water. =owever, chlorides %salt& may still be present and a check might be useful. .he greatest risk for salt deposits is on horizontal surfaces. .he following method utilises the well known principle that chlorides form a milky solution when silver nitrate is added %as commonly used when checking the boiler feed water&.

+bout one mP4 of a suspected tank wall is cleaned by means of cotton wool and distilled water. .he water is filtered through a funnel into a test tube. .he tube is then filled to a total volume of *"" cc with distilled water and well mixed. +nother reference test tube is filled with *"" cc of distilled water. .o both tubes are then added # drops of silver nitrate solution and the tubes well shaken. ,f chlorides are present the sample tube will show a milky appearance. .o the reference tube is then added a standard %known& chloride solution in small amounts by means of a pipette until turbidity is the same in both test tubes. Fith a known chloride contents in the standard solution and a known added amount one can calculate how many grams of chlorides were present on the one m 4 of the tank wall. .he total amount of chlorides in the tank can thus be evaluated. .his amount divided with the tank tonnage gives an idea of increase of chloride contents %if no other sources of contamination occur during the voyage&. ,f the test tube turns out to be too milky for comparison %which means a concentration of above some *"" ppm& its contents can be diluted with a known amount of distilled water and the calculation corrected correspondingly. +S.M #*4 describes in detail a standard chloride determination.

+s an example it can be noted that some specifications allow ", 7 ppm of total chlorides contamination %ethanol&. .his corresponds to ", 7 kg in *""" tons of product. .he permitted increase during transportation is only a fraction thereof. + similar method is used for the determination of chlorides in clear water3soluble products, such as alcohols. .o #" cc of distilled water is added a few drops of nitric acid %=8' 7 & and 4 cc of saturated silver nitrate solution, then mixed with #" cc of the product to be tested, e g methanol. + milky appearance indicates that chlorides are present. Reference tests have to be carried out with the same product with known contents of chlorides if exact values of contami nation are needed. ?.0@ *ater #ontamination 2resence of free water in non water3soluble products can, very roughly be determined on board by the following simple methods. 3 Farm a sample of the product in a test tube or in a bottle.Fater will then collect at the bottom of the tube and can be seen after some time. 3 rop a little of the product on to an electric hot plate. + crackling sound indicates that water is present. $an be used on lubrication oils etc. 'ther methods for non water3soluble products are/ 3 .he product is kept at a temperature slightly above *"" degr. $ for a period of time and is accurately weighed before and after heating %for products with a boiling point above about *4# degr. $&. 3 @se a centrifuge and see if there is any water at the bottom of the test tube. 3 + distillation met3hod according to +S.M G#3;4 % ean Stark& is often used for oil products with relatively high boiling points %fuel oils, gas oil, asphalt, creosote&. + sample is dissolved in xylene and the solution boiled in a glass retort. .he vapours pass through a condensor. .he water condenses and can be measured in a graduated tube. +n accurate determination of water contents can be made with a 56arl3 (ischer5 3 reagent. .his method is suited for laboratory work only. >ery small amounts of water in some products can be observed as a turbidity in a clear liquid when a sample is cooled down to a low temperature %cloud point&. +s a reference calibrated samples are used with known water contents at defined temperatures. .he method is used primarily for chlorinated hydrocarbons such as carbon tetrachloride and trichlorethylene where water might be a severe contaminant also in minute concentrations %example/ for trichlor ethylene a max water contents of e g ", ""; <&. %Remark/ 5cloud point:: also means the temperature at which wax needles may form in certain oils, e g in gas oil, upon cooling. See +S.M

4#""3;;&.

?. 10

( our

(or methyl ethyl ketone %MH6& the presence of water. can be proven by adding a drop of oil. ,f the sample turns a brownish colour there is water in it. +n unusual smell is an indication of cargo contamination and should be reported when it is noticed upon loading. (or normally odour3free products such as glycol, odour may be a severe contamination in itself. ,n order to check products which have a strong 5natural5 odour one can moisten a filter paper with the product and let the liquid evaporate. ,f a strange odour should then arise from the filter paper it is an indication of a contamination %by a product with a higher boiling point than the cargo in question&. ?. 11 Sulp,ur #ontamination <sulp,i es= $ertain products, in particular 5virgin naphta feedstock:: (petroleum naphta& are severely contaminated by minor amounts of sulphides %and also lead compounds&, which poison catalysts in further processing. 2revious heavy oils or dirty harbour ballast water may have left traces of sulphides in the cargo tanks. @sually sulphides are detected by means of a 5copper strip test5, according to +S.M *7"3;#. + polished copper strip is immersed in the product during a period of 4 Q 7 hours at *"" " $ resp #" " $. ,f sulphides are present the copper will become darkened and can be compared with +S.M standard shades where " means no discolouration, , 3 7 increasing discolouration and ! corrosion. @sually, however, the test is use d as a 5yes or no53test without mentioning figures. .he method is easily applicable on board.

+nother less frequently used method uses mercury. + small amount of the product is mixed together with mercury in a test tube. ,f sulphides are present the mercury will become dull in appearance and the product sample turn a brownish colour. .he use of mercury should, however, be avoided. ?. 12 &las, point

.he flash point is a measure to show at what temperature flammable vapours are released in appreciable amounts, .he flash point refers to a defined test equipment and is only a relative measure/ the fact that a cargo is below its flash point does not necessarily mean that the tank is safe against ignition .he flash point for a certain product is defined in its specification. + lowering of the flash point means that the product has been contaminated with a more volatile product, which is a severe contamination. + redistillation of the parcel may become necessary. (lash point lowering is of particular concern with cargoes of type 1et fuel, gas oil, marine diesel oil. (lash point determination is carried out by means of the 2ensky3Martens apparatus described in +S.M G73;; and well known in all petro3chemical laboratories. + product sample is succesively heated and in the vapour space above the liquid a standard ignition flame is introduced at regular intervals until an ignition occurs. .wo methods are used/ open cup %o c& respectively closed cup %c c&. .he latter gives a lower flash point with a difference of # 3 D degr.$. $losed cup is the most commonly used method.

?.13 3istillation range +ny pure liquid has a defined boiling point. $ommercial products often consist of mixtures with also other compounds in accepted amounts. Boiling of a commercial product therefore means that the more volatile components will boil off first and the heavier components later and at a higher temperature. .his results in a range in temperature between commencement of boiling and finished boiling %dry retort&, called 5distillation range5. .he distillation range is defined in the specification for a certain product parcel. eviations indicate that the product has been contaminated. .he test equipment is defined in +S.M *"D9, *!7D and H *773#9. *"" cc of the product is heated to boiling in a retort and the vapours condensed in a water3cooled condensor, see fig. #;. + thermometer is inserted in the vapour stream. .he initial boiling point %,B2& is defined as the temperature at which the first drop is condensed in the condensor. .he final boiling point is read when the retort 1ust becomes dry, dry point % 2&. %(or certain products, particularly gasolines, the final boiling point is read when the last drop leaves the condensor, end point %H2&.& .he distillation range then becomes/ t O ,B2 3 2 %in general& degr.$ or degr.( t O ,B2 3 H2 %gasolines& .his test is used on all hydrocarbons/ alcohols, aromatics, esters, ketones, glycols etc. .he method is best suited for laboratories ashore.

?. 14 Re.ra#ti>e in e+ .his method is based on the property of light to be refracted at different angles3when it passes a prism into different liquids. .his test is realized in an instrument called a refractometer where only a drop of the liquid to be tested is needed to cover the surface of the prism. .he refractive angle can be, me!0sured with good accuracy. .he angle of refraction is a typical property for every pure product. .he method is sensitive to temperature. @sually a standard temperature of 4" " $ is used, but temperature corrections can also be made. Standards are defined in +S.M *D!D3;4. Refractometers are available in laboratory and portable models. .he latter can easily be used on board. .here are tables available against which refractometer readings can be interpreted in terms of concentrations. .he refractive index of a mixture of two products is proportional to the relative contents of the products. .herefore the instrument is suitable to determine strength of solutions, e g sugar in water %molasses&, glycol in water. ,t is also used for the determination of hydrocarbon mixtures %aromatics& and vegetable oils %See British Standard BS ;49374, ;#"3#;, *G#"&

?. 1!

Soli i.ying point eviations indicate that

.he solidifying point %freezing point& is well defined for pure products. contaminants are present.

.he solidifying 2oint is measured by placing a test tube with a thermometer in a cooling bath. .he product is kept stirred and the temperature is read at short intervals. ,t will fall to a minimum and afterwards rise slightly and remain constant for a while. .his temperature is defined as the solidifying point. Hxamples on solidifying points/ Benzene $yclohexane R R #,! degr. $ !,; degr. $

Soyabean oil Sulphur 2henol 2araxylene

R R R R

44,4 degr.$ **D," degr.$ !"3!* degr.$ *7,4 degr. $

'bserve the high solidifying point of benzene and paraxylene. ?. 1$ 'ermanganate7 time test .his is a test to determine contaminants in alcohols and ketones %e g in acetone&. .he method is described in +S.M *7;73;D. 4 cc potassium permanganate solution %conc/ ",4 g 6Mn' dissolved in * litre of distilled water& is added to a #" cc sample in a test tube. $ontaminants in the sample chemically reduce the potassium permanganate which changes colour from red to yellowish. .he time is noted for the sample to assume the same shade as a standard reference solution of coboltchloride3uranylnitrate. + shorter time for this colour change means a greater amount of contaminants. +cetone is tested at 4# " $, methanol at *# " $. .he test tube should be kept dark during the test. +fter some practice this method can be carried out on board, and is in fact already in use in some ships. ?. 1: 0as #,romatograp,y ,n a gas cbromatograph a small product sample is in1ected and made to pass througn a pipe filled with a very fine mineral powder by means of a carrier gas stream %8., = 4S =e, argon&. .emperature is kept constant. .he lighter components will pass through the tube easily but the heavier ones will take more time. ,n this way the components are separated at the outlet where an ion3cell picks up an electric signal which is recorded. Hach product has a typical 5print5. eviations indicate contaminants. .he method is only suitable for laboratory work ashore. + gas chromatograph test from product samples taken prior to loading and upon discharge can tell if contamination has occurred while the cargo was on board. .his method is some times used taking 5fingerprints5 from an oil spill and from a suspected source3in order to establish the origin of a pollution. ?.1? p6 >alue <a#i ity=

+ neutral solution is defined as p=OD. +cidous solutions have p= lower than D and alkaline solutions higher than D %max *!&. Fater soluble products are readily tested by means of litmus paper where a colour change directly indicates the p=3value roughly. .here are also electrode 3meters available where the p=3value can be read directly from a scale. .he p=3value can also be established by means of neutralisation with a sodium hydroxide %caustic soda& solution from which the acidity can be calculated from the amount of alkaline matter added. + colour reagent shows when the solution changes from acidous to alkaline. >egetable and animal oils require the determination of p= value, which indicates the contents of free fatty acids. .his is, in turn, a measure of the quality of the oil, or the degradation of the oil during transport. .he oil is first dissolved in alcohol and afterwards neutralized with sodium hydroxide as indicated above. .he method is described in British Standard BS ;49374, ;#"3#;/*G#". ?. 1@ Ais#osity

>iscosity is measured by means of capillary tubes %+S.M !!#3,2 and +S.M 4#*#& or by an apparatus measuring the friction of liquid between two cylinders of which one is revolving. Measurements on board will rarely be needed. >iscosity is interesting as regards the pumpability of a product. @sually the upper limit for centrifugal pumps is considered to lie around !"" centistoke %cSt&, corresponding to about *#"" Seconds Redwood %sec R& or about #" degrees Hngler % degr.H&. Screw pumps may pump liquids with viscosities as high as *". """34". """ cSt. See conversion table.

?. 20 Spe#tro 7p,otometry + spectro photometer is used to trace minute contaminants %* 3 4 ppm&. 'ne common application is the determination of degree of polymerisation in styrene monomer. .he principle of the instrument is that a product sample is transluced with a light of a known wave length %ultra violet, visible or infra red light&. + certain part of the light is absorbed and does not reach a detector cell. .he amount of absorption is known for pure products. (or common contaminants there are calibration curves available for comparison with readings.

CAR0( 'R(38CT I)&(RMATI()

.hroughout this book examples have been given on the properties of various chemical cargoes. Fhere does the reader find collected information on all likely cargoesK Fhat about new chemical compounds coming on the market every dayK +s mentioned in $hapter , the owner, according to the ,M$' $ode, has the duty to inform his personnel about the hazards involved plus, of course, handling instruc tions. +s regards general product information including, to a certain extent, also trade names, reference is given to ref %*&, %7&, %!&, %#&, %*;&, %*D&, %49&, %!;&. Tuestions about personal safety, the product:s 5hazard profile5 %whether danger upon skin contact or vapour contact, reactivity etc& are treated in ref %*&, %!&, %#&, %7;&. .ank cleaning questions are treated in ref %*"& and %**&. (urther information can be obtained from the manufacturers of chemical cleaning agents. ,nformation on the handling of the cargo including necessary cleanliness, max permitted contaminants etc, is often hard to get. ,n the text some suggestions are made, see also +ppendix # for a selection of common cargoes. 8ever load an unknown cargo identified by only a trade name? ,n the past it has been difficult to obtain a full product information from the makers and from shippers. .hey should have the very best information and should be consulted whenever possible. ,t is hoped that information will be more easily available in the future?

10 10. 01

A)TI7 '(LL8TI() MEAS8RES, S'ILLS, EMER0E)CIES International Con>ention 1@:3

+t an ,M$' conference in 0ondon *GD7 an 5,nternational $onvention for the 2revention of 2ollution from Ships, 1GD7N was drawn up. .he convention has not yet been ratified by the necessary number of -overnments, Fe shall only concern ourselves here with +nnex ,l of the convention/ 5Regulations for the $ontrol of 2ollution by 8oxious 0iquid Substances in Bulk5. .he convention rules that a $argo Record Book shall be kept, ,n certain cases, as detailed below, official 8ational surveyors are required to make entries regarding tank washing etc. for certain cargoes. (or each vessel shall be drawn up a 52rocedures and +rrangementsN book. .he convention divides noxious substances into three categories / a& $ategory + 3 Substances which if released into the sea from tank cleaning or deballasting operation would present a ma1or hazard to either marine resources or human health or cause serious harm to amenities or other legitimate uses of the sea and therefore 1ustify the application of special measures to prevent their escape into the marine environment. Substances of $ategory + are bioaccumulated and liable to produce a hazard to aquatic life or human healthE or are highly toxic to aquatic life. Hxamples of $ategory + substances/ acetone cyanohydrine, acrolein, carbon disulphide, creosote, cresols, dichlorbenzene, sodium pentachlorophenate, tetramethyl lead. b& $ategory B 3 Substances which when released into the sea from tank cleaning or deballasting operations may present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses of the sea and therefore 1ustify the application of special anti pollution measures. Substances of $ategory B are bio3accumulated with a short retention of the order of one week or lessE or are liable to produce tainting of sea foodE or are moderately toxic to aquatic life. Hxamples of $ategory B substances/ acrylonitrile, allyl alcohol, carbon tetrachloride, chlorobenzene, ethylene dibromide, phenol, trichlor ethylene. c& $ategory $ 3 Substances which when released into the sea from tank washing and deballasting operations may present a minor hazard to either marine resources or human health or cause minor harm to amenities or other uses of the sea and therefore require special operational conditions. Substances of $ategory $ are slightly toxic to aquatic life and include additicrnally certain substances which are practically non3toxic to aquatic life. Hxamples of $ategory $ substances/ acetaldehyde, acetic acid, allyl chloride, amyl acetate, benzene, chlorosulphonic acid, cumene, cyclo hexane, ethylbenzene, ethylene diamine, nonyl phenol, octanol, sodium hydroxide %caustic soda&, styrene monomer, sulphuric acid, vinyl acetate, xylenes. .he following substances are excluded from the $onvention requirements as causing negligible harm %+ppendix ,,, to

Category A

is#,arges

.he convention rules that discharge into the sea of substan ces of $ategory + shall be prohibited. .ank washings are to be pumped to a receiving facility until the washings have a concentration of less than ", * < in the $ategory + examples above %", "* < for carbon disulphide& and the tank is then empty . .hereafter the tank may be flushed to min # < of tank capacity and the water may then be discharged into the sea if all of the following conditions are satisfied %$ategory +&/ a& Ship:s speed greater than D knots b& 5+dequate dilution5 in ship:s wake to be proven to satisfaction to the +dministration %reliable calculations or references to experiments& c& ischarge below the waterline, taking into account the location of sea water intakes d& ischarge not less than *4 8M from the nearest land at a depth of water not less than 4# metres. Category 2 is#,arges

Substances of $ategory B, contaminated ballast water or tank washings containing these substances shall be prohibited to be discharged into the sea. =owever, such mixtures may be discharged when the following conditions are fullfilled %$ategory B& / a& Ship:s speed greater than D knots b& $oncentration in ship:s wake shall be proven by reliable calculations not to exceed * part per million c& .he maximum quantity of cargo discharged into the sea from each tank and ass. piping does not exceed * m 7 or *A7""" of tank capacity, whichever is the greater. d& +s c& above e& +s d& above Category C is#,arges

Substances of $ategory $, contaminated ballast water or tank washings containing these substances are prohibited to dis charge into the sea. =owever, such mixtures may be discharged when the following conditions are all fullfilled %$ategory $& /

a& Ship:s speed greater than D knots b& $oncentration in ships wake shall be proven by reliable calculations not to exceed *" parts per million c& .he maximum quantity of cargo discharged from each tank and ass. piping not to exceed 7 m P7 or *A*"""" of tank capacity, whichever is the greater d& +s c& for $ategory + e& +s d& for $ategory + .he $onvention further describes 5Measures of $ontrol5 saying that each -overnment shall appoint or authorize surveyors whose duties shall include surveillance according to this $onvention. 'ther measures of control/ 3 $ategory + substances/ .he Master shall make entries regarding tank unloading and all cargo operations in the $argo Record Book including concentrations of cargo in tank washings to be dischargedE the latter also to be certified by the above surveyor. +s further stated in the $onvention the surveyor may satisfy himself that for $ategory + substances alternative procedures for pre3cleaning and direct calculation of maximum cargo remaining on board may be acceptable, provided no more pollution occurs other than ruled for $ategory + above. +ll such deviations from the strict $onvention rulings to be entered in the $argo Record Book together with all relevant calculations etc. 3 $ategory B and $ substances/ .he Master shall enter in the $argo Record Book when a tank is unloaded, piping systems drained and when he has ascertained that the amount of cargo left on board after unloading does not exceed the amounts allowed and necessary dilutions achieved etc %see above&. Such observations and entries may be checked by the surveyor. .he Master shall further record internal transfer of cargo, discharge of washings according to regulations as well as disposition of tank washings if cleaning is carried out in port, Residues from slop tanks and pump room bilges shall be treated equivalently with cargo from the cargo tanks. .he $argo Record Book shall be completed on each occasion and for each tank whenever any of the following operations take place/ 3 loading of cargo 3 transfer of cargo during the voyage 3 discharge of cargo 3 transfer of cargo, cargo residues, etc to a slop tank 3 cleaning of cargo tanks 3 discharge of slop tanks 3 ballasting of cargo tanks 3 discharge of ballast water discharge or escape of cargo or cargo mixtures .he $argo Record Book shall be signed on each page by a responsible officer and the Master. .he book shall be kept readily available on board. + chemical tanker shall be surveyed by the relevant +dministration with regard to this $onvention and after compliance obtain a ::$ertificate of (itness for the $arriage of 8oxious $hemicals in Bulk5. .he $ertificate shall be endorsed with details of approved washing procedures and approved discharge arrangements for tank washings. 10.02 Spills, emergen#ies

Ship design and operational routines all aim at reducing the risk for environmental pollution. 8evertheless/ accidents can happen or be caused by improper action by anyone involved on board, ashore or by other ships. .raditional thinking rules that the vessel and her cargo should be salvaged on the basis of the values they represent. Fith chemical and oil cargoes this is not necessarily true. ,t is more a matter of containing the cargo on board or by other means until the situation can be mastered with due regard to weather, shipping etc.

Spills of any size in port, due to over3fillings, hose break age etc, should be reported to the 2ort +uthorities at once. 6eep in mind that water supplies, other water intakes local fishing, public amenities etc can be affected with enormous human and economical consequencies unless immediate counteractions can be taken. ,n order to reduce the danger for minor spillages deck scuppers should be closed, drip pans arranged under hose manifold and a close watch kept when topping up the cargo tanks. Fithin ,M$' work is in progress on defining ::danger profile5 for various substances with regard to, among other things, what action is to be taken after spills in shore areas, estuaries etc. (or the time being information on how spills are to be treated must be sought from 2ort +uthorities, who will normally take charge of a spill situation. See also ref %4!& where various chemicals are rated with regard to the effect on marine life and aesthetic effects. $ommon cargoes which are particularly damaging to marine life when released to the sea/ acetone cyanohydrin, acrolein. Strongly negative aesthetic effects will be caused by the release of/ aniline, creasote, dodecyl benzene, acrolein, acetone cyanohydrin. 10. 03 Controlle is#,arge o. < no+ious= tan" 4as,ing

(irst and foremost the cargo tanks and piping shall be dischargect as completely as possible, taking into account/ 3 Ship to have beneficial trim and list to assist final stripping. - $argo to have correct temperature for easy flow to pump suctious. 3 +d1oining tank walls %Ocargoes& as far as possible to have a temperature which reduces noxious cargo under discharge to cling to the walls. 3 2ossibilities to drain the piping system by blowing ashore with air or inert gas or use stripping line of small diameter ashore. Studies and calculations have been made for many individual ships and products to demonstrate that the amount of cargo remains from the various tanks, using above procedures and other particular methods, will not exceed the Mpermissible amounts for B and $5 %* m P7 or *A7""" arid 7 m P7 or *A*""" of tank volume&. Similarly, pumping procedures for overboard discharge %pumping speed and discharge pipe arrangement& have been established for many vessels in order to fullfill requirements of dilution in the ship:s wake. ,n some ships special 5mixing tanks:: are provided. By means of mixing pumps cargo remains are diluted with seawater to permissible concentrations.

11

7 CAR0( C(M'ATI2ILIT1 A)3 REACTIAIT1

11.01

Compati%ility

Between some chemicals violent reactions may occur if the chemicals are mixed in certain proportions. .he result may possibly be an eruption and tank rupture. Such an occurrance must be prevented. Fater may also have to be considered in this respect. 0eakages through bulkheads occur at times in any tanker. 8ormally, however, 3such leakages are only minor seep ages. .hey will not cause any violent reaction due to the great disproportion in mixture from dangerous proportions. But legislation as expressed in the ,M$' $hemicals Bulk $ode ref %4#&, and in the @S $oast -uard Rules ref %*9& and +ppendix 7 expressly prohibits the placement of inter3reactive cargoes on both sides of a bulkhead. .here must be an empty tank, a cofferdam or a tank with a cargo neutral to both products in between. .his requirement causes some headaches in cargo planning. 5 iagonal contact:: between tanks is normally considered as sufficient separation between reactive cargoes. More important, however, is the complete separation of piping systems so that one product cannot inadvertently be pumped into another. .o this effect strategic pipe bends may have to be removed and blind flanges fitted on each pipe end. Modern chemical tankers will have blind flange valves fitted, one type of which is shown in fig *7. Such a blind flange valve must have a double separation between the products with a drain in the interspace. + single blind flange is not acceptable. Remember also to separate drain lines or slop connections to avoid the possibility of cargo mixing. .he cargo inter3 reactions may be of type/ 3 a& $hemical reaction/ Strong % inorganic& acid plus alikali %or water& causes heat, e g sulphuric acid plus caustic soda or water. .herefore sulphuric acid may not be carried in tanks bordering the side shell or filled ballast tanks. Similarly sulphuric acid may react with a number of hydrocarbons except parraffines %petroleum oils&. +mines % aniline, diethylamine& may react with esters % butyl, acetate, ethyl acetate&. $austic soda will react violently with acrolein, acrylonitrile and allyl alcohol. 3 b& 'xidation/ +n 'xygen3rich compound like propylene oxide may react with an amine %e g diethylamine& or an aldehyde %e g acetaldehyde&. +n ether %e g ethyl ether& may react with oxygen and from a peroxide which is an explosive hazard. .he ether should be inhibited and carried in an inerted %8 4 & tank. 3 c& +uto3 reaction/ See **. "4 3 ,nformation about dangerous cargo combinations can be found in the data sheets in ref %*&, in the @S $oast -uard $ompatibility $hart %with amenaments and exceptions& reprinted in +ppendix 7. 11. 02 Auto7 rea#tion $ertain hydrocarbons compounds have a tendency to polymerize with time, accelerated by heat, light, sometimes air or other matter such as rust. 2olymerization means that several molecules of the same kind binding together to bigger molecules. .he compound tends to become more viscous or eventually solidify. =eat is liberated , which accelerates further polymerization. $hemically most cargoes are monomers, which means that they, before any polymerization, consist of single molecules. Hxamples on polymerization products commonly shipped in chemical tankers/

acrylic acid acrylonitrile butyl acrylate butyl methacrylate decyl acrylate ethyl acrylate ethylhexyl acrylate isoprene methyl acrylate methyl methacrylate styrene %monomer& vinyl acetate vinyl chloride vinylidene chloride ,n order to prevent or delay polymerization certain inhibitors are added to the product before loading. .he inhibitors are being consumed with time, usually accelerated by increased temperature. ,t is hardly possible in practice to add more inhibitor during the voyage. ,M2'R.+8./ check with the shipper 3that enough inhibitor has been added and request a $ertificate of ,nhibition before loading? .he inhibitor consists of various substances depending on the product. +s examples can be mentioned/ 2roduct acrylonitrile styrene monomer vinyl acetate vinyliciene chloride acetone cyanohydrin ,nhibitor paramethoxy phenol 2aratert butyl catechol %2.B$&, hydroquinone hydroquinone, diphenylarnine paramethoxy phenol, thymol, 2henol ,norganic acid

,t is possible to check the contents of inhibitor in the product, usually by relatively simple means. + test for inhibitor contents in styrene consists of mixing one part of styrene with three parts of methanol. ,f the mixture remains clear or slightly bluish the product is intact. + slight whitish turbidity indicates polymerization and that the inhibitor probably is consumed. +sk the shipper to deliver on board a kit for inhibitor check for the product to be loaded. ,n order to take good care of polymerizable products, remember/ 3 6eep the product as cool as possible. 8ever place close to heated cargoes? 3 6eep hatches closed to avoid unnecessary light. 3 $heck cargo temperatures regularly. ,n the event of an unexplicable temperature rise/ consult the shipper and the shipowner and discuss possible action. .o 1ettison might be a last resort. +cetone cyanohydrin decomposes with time, accelerated by heat. + stabilizer should be added consisting of an inorganic acid. 'ther precautions are similar to those for the products above. 11.03 To+i# >s e i%le pro u#ts

.oxic products must never get mixed into edible products for human or cattle feed? ,n this case minor seepages

between tanks might prove disastrous. Strangely enough the ,M$' $hemicals Bulk $ode does not rule on this point, however, in ref %*&, chapter G. 4. 4 the matter is mentioned. IMPORTANT / Hdible products should never be loaded with bulkhead to bulkhead contact with toxic cargoes? .he piping systerns should be entirely segregated or provided with double blind flanges.

12

CAR0( 'LA))I)0 ETC

+ check list is given below, which might be useful when discussing cargo planning in your ship. .he order of the points is of no importance. *& 0oad the vessel so that positive trim is ensured during discharge, preferably without filling ballast in cargo tanks, particularly not in port. .ry to find out the receiver:s desired sequence of discharge. 6eep an eye on hogging Asagging? ,nter3reactive cargoes must not be placed in neighbouring tanks. 2iping systems must be separated by double blind flanges to prevent erroneous handling of valves. $heck the cargoes with data sheets in ref %*& and +ppendix 7 for cargo compatibility. .oxic cargoes must not be placed in neighbouring tanks with edible products %human or cattle&. Separate the piping systems by means of double blind flanges

4&

7&

!& $heck with the tank coating manufacturer:s list of permissible cargoes for coatings in each tank. .he general rules are/ Iinc silicate coatings are resistant to strong solvents %aromatics, alcohols, ketones etc&. Iinc silicates are not resistant to caustic soda or alkaline cleaning chemicals. Hpoxy coatings are resistant to petroleum products, caustic soda, vegetable oils, wine, seawater, fatty acids, limited resistance to alcohols and aromatics. $oal tar epoxy is resistant to sea water, crude oil and petroleum products in general but should not be used for 1et fuels or light oils as they tend to be contaminated by bleeding tar. #& ,n certain cases the tank coating manufacturer gives a limited acceptance for a product %time andAor temperature&. +void then placing heated products on the otherside of the bulkhead. 0et epoxy weather out properly after solvent cargoes. o not fill ballast water immediately after methanol in the same tank. ;& 2olymerizable products %e g styrene, vinyl chloride& should never come in bulkhead contact with heated cargoes. .he same refers to drying vegetable oils %e g linseed oil& . D& >olatile products %aromatics, ketones, alcohols etc& should not be put into bulkhead contact with heated cargoes in order to avoid unnecessary evaporation losses. 9& .he cargo tanks are normally inspected and approved prior to loading. .his does not necessarily relieve the vessel of responsibility for contaminations. .he masterA owner carries the responsibility in taking due care of the cargo. .o protect ones own interest the vessel:s own inspections should be recorded in the deck log. G& +fter cargoes with a strong odour %fish oil, phenol, octanol, tall oil, turpentene, molasses& the tanks should not be used immediately for odoursensitive cargoes such as glycols, ve getable oils, *"& +fter leaded gasoline, cargoes for human or animal consumption must not be loaded as the next cargo, neither 5virgin naphta feedstock5. 0ead compounds may adhere to the bulkheads after several intermediate cargoes even in coated tanks. Fine cargo may dissolve lead remains, which are many intermediate cargoes ::old5.

**& ,n case of doubt of purity of cargo to be loaded/ take cargo samples also from the loading manifold upon loading and have them sealed and identified for future reference. *4& ,n tanks which have contained products with a high boiling point andAor low water solubility %e g lubrication oils& there will be minute amounts of cargo left after washing. .hese tanks are then not suitable for a ::sensitive5 cargo such as methanol. *7& $onsult the cargo trim and stability book. .here may be restrictions with regard to cargo distribution and stabllity in hypothetical damaged condition. *!& Fhen one and the same pipe has to be used for several consecutive products/ Start with the lighter products, going on to more viscous ones. .he pipe may have to be drained and steamed in between, therefore try to arrange an open loop. .he most sensitive cargoes may have to be loaded 5over top5 through the hatch. ouble valves are usually not considered as a sufficient means of segregation in the chemical trade. Blind flanging is necessary. 2rovisional blind flanges can be made of 4 3 7 mm sheets, preferably stainless steel. 'bserve/ reactive cargoes need a more substantial segregation, see 4& and also 7& above. *;& Fhen two cargo parcels cannot be segregated by means of blinds the liquid level can purposely be kept higher for one of the products, thereby ensuring that any possible leak will go in the less dangerous direction with regard to contamination damage. *D& $heck cargo valves for tightness prior to loading and take leaking valves into consideration when placing cargoes. *9& Blow heating coils over deck prior to loading to ensure that no cargo has leaked into them which could cause danger in the engine room when heating is commenced. 2ressure test the coils before loading. *G& =eating coils %steam& should be blind flanged towards the engine room when products are carried which do not require heating. 4"& Before loading water3sensitive cargoes %halogenated compounds, e g trichlor ethylene& or chloride3 sensitive cargoes %alcohols, glycols&/ hose test the tank hatches for tightness and check valve spindle glands on weather deck. 4*& ,nform the 'wner if there seems to be a disagreement between BA0 product and the product actually loaded %may affect freight, cleaning costs, safety&. 44& +void carrying the most toxic products as last cargoes before dry3docking and shipyard work. *#&

RE&ERE)CES * .anker Safety -uide %$hemicals&. 7 vol. ,nternational $hamber of Shipping. 0ondon *GD*. 7"374 St Mary +xe, 0ondon, H$7+ 9H.. .anker Safety -uide %2etroleum&. ,nternational $hamber of Shipping. 0ondon *GD". 7"374 St Mary +xe, 0ondon, H$7+ 9H.. =andbuch der gefdhrlichen -titer. Springer *GD". $hemical Safety ata Sheets. Manufacturing $hemists +ssoc. %M$+& Fashington $.

7 ! # ; D 9

$hemical ata -uide for Bulk Shipment by Fater. %@S$- $- 799&. @S $oast -uard. -overnm. 2rint. 'ff, *GD;, 7*D pp. 6emisk Skyddshandbok S+(, Svenska +rbetsgivarfbreningen, Stockholrn *G#9. Safety in industry. Maritime safety data. @S ept. of 0abour. Bull 7"!. 8ational (ire 2rotection +ssociation =azardous $hemicals ata 8(2+ nr !G, 8(2+ Boston, Mass. ,nt. 'il .anker and .erminal Safety -uide %,'..S-& ,nst. of 2etroleum, ;* 8ew $avendish Street, 0ondon F,M 9+R. .ank3cleaning -uide %4 ed& $hemical 0aboratory r + >erwey, $oolhaven, Rotterdam.

*"

** *4 *7 *! *#

>ecom .ankcleaning >ecom ,nternational, +ntwerp. Bulk shipment of some ,$, products. ,$, Hngland. 2henol handling and storage. $erechlor bulk storage and handling. ,$, Hngland. 0iste over yrkeshygieniske grenseverdier Lrkeshygienisk ,nstitutt, 'slo. .hreshold 0imit >alues of +irborne $ontaminants and 2hysical +gents. +m. $onference of -overnm. ,ndustr. =ygienists. 2.'. Box *G7D, $incinnatti, 'hio !#4"*. Sax, 8 ,rving, Hd. angerous 2roperties of ,ndustrial Materials. 7rd ed.. 8ew Lork, Reinhold *G;9, *4#* pp. Marsden, $. Hd. Solvents -uide. 0ondon, $leaver3=ume, ;77 pp. $ode of (ederal Regulations, !; $(R *3;#, !; $(R, ;;3*!#, !; $(R *#"3*GG. .he Superintendent of ocuments, @S -overnment 2rinting 'ffice, Fashington $ 4"!"4. %Revised edition every year&. (ristedt, B, Lrkesmedicin Studentlitteratur, 0und *GD*, G; pp. Moeschlin S, 6linik und .herapie der >ergiftungen -eorg .hime >erlag, Stuttgart, D#" pp. Firth 8, =echt -, -loxhuber M, (ibel, .oxikologie 4 ed, -eorg .hime >erlag, Stuttgart, 7G* pp. 2atty (, ,ndustrial =ygiene and .oxicology ,nterscience 2ublishers ,nc, 8ew Lork %4 vol&. 8avigation and >essel ,nspection $ircular 8o #3D" 5-uide to $ompatibility of $hemicals5 %with exceptions&. @S $oast -uard, Fashington $ 4"#G* %expected revised late *GD!&. Hvaluation of the =azard of Bulk Fater .ransportation of ,ndustrial $hemicals %.entative guide&, 8ational +cademy of Sciences, Fashington $, *GD4, 7" pp.

*; *D *9 *G 4" 4* 44 47 4! 4#

$ode for the $onstruction and Hquipment of Ships $arrying angerous $hemicals in Bulk % ,ncl +rnendrnents * 3G&, ,nter 3-overnmental Maritime $onsultative 'rganization %,M$'&, *3" * 3 *"! 2iccadilly, 0ondon F *> '+H. 4; 4D 49 '+H, B,M$=HM>'L >oyage $harter 2arty. (r. - 6nudtzen 0td, ## .oldbodgate, $openhagen. +nvisningar om behandling av fbrgiftningar uppkomna vid transport av farligt gods, sasom kemiska bekampningsmedel. S1bfartsverkets Medd. *GD4 +/*; ,nternational Martime angerous -oods $ode %,M - $ode& ,nter 3-overnmental Maritime $onsultative 'rganization %,M$'&, i'l3i'! 2iccadilly, 0ondon F,>

*GD4, 7 vol. 4G $ode of 2ractice for the Safe $arriage of angerous -oods in (reight $ontainers, .he $hamber of Shipping of the @6, 7"A74 St Mar +xe, 0ondon H$7+ 9H.. 61emikaliefart 8orges Rederforbund3 Skip sfartens +rbeidsgiverforening, 'slo *GD4 angerous -oods in =arbours etc. 8otice %*GD4 +/*4& of the Swedish +dministration of Shipping and 8avigation. Huropean agreement about ,nternational transportation of dangerous goods by road %+ R&. ,nternational regulations about transportation of dangerous goods by railway %R, &. .he ,+.+3 regulations relating to the carriage of restricted articles by air %R+R&. $ertain Bulk angerous $argoes, Special ,nterim Regulations for ,ssuance of 0etters of $ompliance

7" 7* 74 77 7! 7# @S 7; 7D 79

epartment of .ransportation, $oast -uard, (ederal Register >ol 79, 8o **#, June *GD7. Medical (irst +id -uide for @se in +ccidents ,nvolving ,M$', F=', ,0', ,M$' sales 8o *GD 7/7%H&, 0ondon. angenous -oods

Symposium om regler og foreskrifter for k1emikalieskip. ,nformation 8o **, June *GD7, et 8orske >eritas, 'slo. ,nternational $onvention for the 2revention of 2ollution from Ships, +nnex , %'il&, +nnex ,, %$hemicals&, *GD7, ,M$', *"*3*"! 2iccadilly, 0ondon F,> '+H. ruckerei -mbh, =amburg

7G Stowage and Segregation to ,M$'3$ode 6. ". Storck U $o >erlag und *GD7. !" !* !4 Stainless Steel for $hemical .ankers +vesta Jernverk +B, DD! "* +vesta, Sweden.

Recommended 2ractice for escaling and $leaning Stainless Steel Surfaces. Sect. ,,,, Bull. H, .he ,nt. 8ickel $o ,nc, ;D Fall Street, 8ew Lork #, 8.L.

Rules governing the design of chemical tankers are included in the Rule Books of the $lassification Societies/ +merican Bureau of Shipping, Bureau >eritas, et 8orske >eritas, -ermanischer 0loyd, 0loyds Register of Shipping. !7 -as Hvolution/ .anker and .erminal Safety. .he ,nstitute of 2etroleum, ;* 8ew $avendish Street, 0ondon F,M 9+R, *GD*. $lean Seas -uide for 'il .ankers ,nt. $hamber of Shipping, 'il $omp. ,nt. (orum, *GD7, 0ondon. Monitoring of 0oad3on3.op

!!

!#

,nt. $hamber orf Shipping, gil $omp. ,nt. (orum, *GD7, 0ondon. !; !D !9 !G #" $ondensed $hemical ictionary, rev. by -essner U =awley >an 8ostrand Reinhold, 8ew Lork. =andbook of Hmergency .oxicology, 6aye. +rticles on 5.anker cargo handling5 5Skip5 8o 9, *G;# 'slo. $hemical carriers and their tanks, 0es Streeter, .anker U Bulk $arrier, +ugASept *GD!.

.oxic and =azardous ,ndustrial $hemicals Safety Manual. .he ,nternational .echnical ,nformation ,nstitute, .oranomon3.achi6awa Bldg *3;3#, 8ishi3Shimbashi, Minato3ku, .okyo *"# Japan. #* 5$hemical .ankers 3 .he Ships and the Market5 by M. $orkhill. + (airplay report. (airplay 2ublica3 tions 0td. , 2udding 0ane, 0ondon H$7R 9++. 5Safety in $hemical .ankers:: ,nternational $hamber of Shipping. 7"374 St. Mary +xe, 0ondon H$7+ 9H.. =ygieniska gransvdrden %.reshold limits values& +rbetarskyddstyrelsens anvisningar nr *"" %*GD9& 0iber (orlag, S3*;4 9,G >allingby, Sweden. 5$hemlog 3DG:: Resistance list for stainless steels @ddeholm, (ack, S3;G7 "* egerfors, Sweden.

#4 #7

#!

## Rules and Regulations for (oreign >essels 'perating in the :8avigable Faters of the @nited States. @S $oast -uard, , ec. *GDD 2art *#7, $-3#f# Superint. of ocuments, @S -overnment 2rinting 'ffice Fashington $, 4"! "4 #; 'ilseeds, 'ils and (ats %second Hd. ,nt +ss. of Seed $rushers .ransport and Tuality Sub3$ommittee. #D .dtning och ,nvallning % Sealing and $ontainment of Spills& %Swedish& Svenska Brandf;rsvarsf;reningen 6ungsholms =amnplan 7, **4 4" Stockholm

A''E)3ICES

A''E)3I/ I

TA2LE (& 'R('ERTIES (& S(ME C(MM()L1 S6I''E3 'R(38CTS Hxcerpt from/ 5.he carriage of special liquid cargoes5 by Hgil +brahamsen et 8orske >eritas 2ublication nr !#

A''E)3I/ 2

C6EMICAL 3ICTI()AR1 E/'LAI)I)0 S(ME C(MM() TERMS

+cid number required for measure of free acids +lcohol +lcohols may they contain +ldehydes position hydrocarbons %e g +lkyl +liphatic structure. +lkanes %alcynes& # =*4 +mines by one, +ntifreeze +romatics carbon atoms benzene, +tom properties and can take part

%neutralization number& 8umber of milligrams of potassium neutralization of free fatty acids

hydroxide

present in , g of fat or oil, a radicals %'=&.

present in a substance. 'rganic compounds containing one or several hydroxyl

be mono3, di3, tri3, etc according to the number of hydroxyl radicals and primary, sec. , or tert. according to position of hydroxyl radical. + group of organic compounds containing the Q$=' radical and holding a between alcohols and acids. .hey are produced by the oxidation of alcohols& and can be used for production of alcohols. Hxample/ acetaldehyde %$= 7 $='& + non3cyclic saturated hydrocarbon of general formula

$ n = %4n R*&

'rganic compounds in which the carbon atoms are not arranged in a ring +liphatic saturated hydrocarl3&ons of type $n=%4n R 4& Hxample/ 2entane $ Substances derived from ammonia where the hydrogen atoms are replaced two or three alkyl groups. @sually glycol derivatives. +romatic hydrocarbons %benzene hydrocarbons&, unsatu rated, with the in rings with a ; carbon nucleus ring. Hxamples/ aniline, naphtalene, toluene, xylene. .he smallest particle of an element which retains the characteristic

behaviour of the element, the smallest particle of an element which in a chemical reaction. Brix degree indicates that ; " $. + $arbinol 5$arbitol5 $arbonyl group $arboxyl group $ellosolve derivatives. measure of specific gravity S- O !"" * !"" 3 degrees Brix *& Synonym for methyl alcohol 4& $ompounds of similar structure as *& obtained by substitution processes. .rademark for a group of mono and dialkyl ethers of diethylene glycol. .he group.$' which is a characteristic of aldehydes and ketones. .he characteristic part of most organic acids, e g fatty acids. , .he per cent by weight of soluble solids in a syrup at ;9 " (. V " Brix the solution to which it refers contains Vgm of sugar in *"" ml at *#,

.rade mark for mono3 and dialkyl ethers of ethylene glycol and their

Fidely used as industrial solvent. $hlorination erivative reactionE an which it is derived e g benzene derivatives containing the benzene ring. etergent owanol making utrex generally of low Hlement Hster organic acid. solvents. Hthanol (atty acids frequently in fats common in animal and vegetable tissue and are obtained by boiling or extractionE they are used in edible -lycerid -lycerol %-lycerine& $olourless printer:s ink, -lycols glycol, polyesters, =alogens $ombined 8a$l&. =ydrocarbons with hydrogen or halogens and comparatively indifferent to chemical action. 0iquid cosmetics. .he chemically related elements fluorine, chlorine, bro mine and iodine. with hydrogen they form acids %e g =$*& and with metals salts %e g $ombinations of carbon and hydrogen. .he most important/ 3 2araffinsE saturated aliphatic hydrocarbons incapable of combining further explosives, cosmetics. +liphatic secondary alcohol compounds containing 4 Q'= groups. Hthylene colourless liquid, produced from ethylene %oxide&. +ntifreeze, used in oils and fats, soap manufacture etc. +n ester derived from glycerol. .he fats and oils are mainly triglycerides of fatty acids, e g tripalmitin. +lcohol which combined with %ester& fatty acids is a constitu ent in fats. sweet syrup used as plasticizer, solvent and reagent in paints, $leaning agent. .rade mark for a series of glycol monoethers used as solvents and plasticizers. .rademark for a series of aromatic hydrocarbon concentrates, volatility. @ltimate constituent of matter. .here are *"7 known elements. +n organic compound %salt& formed from an alcohol %base& and an Many esters occur in nature, e g fats. Many esters are important as Hthyl alcohol %spirit, spirit of wine, grain alcohol, absolute alcohol&. 'rganic monobasic aliphatic acids. .he three acids occur ring most as glycerol esters/ palmitic stearic and oleic acids. (atty acids are .he treatment with or introduction of chlorine into a compound. + compound obtained from another compound by a simple chemical organic compound containing a structural radical similar to that from

paraffins soluble in alcohol and ether but not in water. 3 'lefin or ethylene series, unsaturated hydrocarbons. Hxample/ propylene %gas&. 3 $ycloparaffin %naphtene& serie have saturated ring hydrocarbons. Hxamples/ cyclopentane, cyclohexane. 3 Benzene hydrocarbons. Hxamples/ benzene, toluene, xylene. 3 .erpenes, unsaturated hydrocarbons. Hxample/ turpentine oils. .o introduce hydrogen into a molecule, as the saturation of unsaturated + chemical reaction in which water reacts with another substance to form more new substances %e g 5hydrolyzable solvents*such as acetates, esters, halogenated compounds %often chlorinated& may with water form organic or =ydroxyl group in.alcohols and ,nhibitor down or polymerization. ,S'3 ,somer compound yet which result different physical and chemical properties. 6etones and ethyl ketone. Methanol Mineral acid Mineral oil Molecule Mono3 Monomer conversion into n3 Methyl alcohol Strong inorganic acids e g sulfuric, hydrochloric, nitric and phosphoric acid. Mixture of liquid hydrocarbons obtained from petroleum. .he chemical combination of 4 or more like or unlike atoms. + prefix indicating ::one5. + molecule or compound usually containing carbon which is capable of polymers, plastics, synthetic resins by combination with itself. + prefix indicating ::normal5, usually a straight chain. + class of organic bodies produced by oxidation of secondary alcohols characterized by the carbonyl group %$'&. Hxamples/ acetone, methyl inorganic acids. .he radical '=3group %oxygen and hydrogen&. ,s a charac teristic patt

=ydrogenate compounds. =ydrolysis one or

phenol. -eneral term for compounds or materials that have the effect of slowing stopping undesired chemical changes such as corrosion, oxidation or + prefix indicating a similarity. .he property of having the same percentage composition as another

differing in relative position of the atoms within the molecule from

'lefins

+ class of unsaturated hydrocarbons. .hey are characterized by relatively great chemical activity. Hxamples/ propylene, ethylene. See mineral oil. See alkanes. .rademark, for a series of lubrication oil additives for im proved anti3wear, temperature detergency etc. .rademark, for a. series of lubrication oil additives for im proving viscosity %petroleum 1elly, >aseline& 2urified mixture of semisolid hydrocarbons. ,ngredient which is added to a plastic to soften increase tough ness or properties of the binder, e g camphor, trioresyl phosphate. + substance c? giant molecules composed by sirnple molecyles %monon3ers& in numbers. .he formation of a polymer from a monomer. 2olymerization is an undesired storing and transportation. 2olymerization is accelerated by the presence of

2araffin oil 2araffins 2aranox high 2aratone index. 2etrolatum 2lasticizer otherwise modify the 2olymer great 2olymerization process in heat, light, some

acids, sometimes rust or other compounds. Safflower oil Saturated compound substances by Solvent dissolving other naphta, carbon Solvesso Stoddard Solvents flash point .all oil tetrachloride, turpentine, carbon disulphide, cyclohexanol, toluene, xylene. .rademark for a series of hydrogenated naphtas used as solvents. %safety solvent& + petroleum distillate used mainly in cleaning with limits to max and boiling point temperatures. 0iquid resinous saponifiable oily by3product of the sulfite process. + drying vegetable oil, +ll valence bonds of the elements are satisfiedE incapable of absorbing addition. ,n chemicals trading usually the name for products used in industry for substances. Hxamples/ acetone, alcohols, glycols, benzene, petrol %gasoline&,

APPEN I! " I)&(RMATI() () T6E 6A)3LI)0 (& S(ME C(MM() CAR0(ES 0isted in this appendix are some of the common products in chemicals trading. ,nformation on necessary tank cleanliness, cargo handling on board, materials etc are also given. .he information contained in this +ppendix, however, does not take into account toxity, reactivity with other products or safety regulations. .his type of information can be found in other literature, in particular in ref %*, 4, 7, !, #, 9, G, *7, *#, *;, *D, 47, 4#, 7;, !;&.

Hvery opportunity must be taken to obtain additional information from the shipper, terminal operators etc? iscover for what purpose the cargo in question is intended. 'ne and the same product may have more or less stringent requirements on cleanliness depending on its future use. $hemical cargoes in general require that the tanks are completely dry and clean, pumps, valves and piping well rinsed and drained before loading. ,n the following pages tank cleaning is commented upon only when particularly stringent requirements apply or when some unexpected rules apply. Regarding tank cleaninp in general see $hapter D. .he necessity of taking properly sealed and identifiable cargo samples is important, see $hapter 9."* $'8.H8.S +cetic acid +crylonitrile +mmonia solutions +sphalt Benzene Butyl acetate Butyl alcohol Butyl glycol $arbon Black (eedstock $austic soda $erechlor $resol $yclo3=exant etergents Hthyl acetate Hthyl glycol Hthyl glycol acetate 43Hthyl =exoic acid -lycols %general& 0atex Methanol 8onyl phenol 'ctanol 2ara3xylene 2henol 2hosphoric acid Styrene monomer Sulphuric acid, conc .oluene, Vylene >egetable oils ACET C AC D .oxity/ .oxic, see ref %*&, %!&, %*;& $argo =andling./ .o be kept at min R*D " $. =eating coils to be of stainless steel %or aluminium&. Materials / Mild steel is normally not acceptable. $oatings of epoxy, zinc silicate or phenolic resins are not acceptable.

.anks of stainless steel are normally used. +$RL0'8,.R,0H %5+8::& .oxity / >ery toxic, see ref %*&, %!&, %*;&. $ontamination / 0ight causes polymerization and darkening of the product and should be avoided. Fater should be avoicieu as it may inactivate the inhibitor added to the product. .ank condition prior to loading/ .anks and piping must be completely dry and clean. $argo handling / 0oading of ship:s tanks should preferably be arranged with cargo vapour return to shore tanks. 6eep all tank lids closed. 'nly closed gauging system should be used. Blind flange cargo and vapour piping to other tanks. o not place acrylonitrile with bulkhead to bulkhead contact with edible products. Blind flange heating coils. =eating coils to be blown through over deck prior to being taken in use again. +void entering pump rooms as much as possible during cargo transfer. 6eep pump rooms well ventilated. .ank cleaning./ Fash the tanks thoroughly with cold seawater. Steam and ventilate the tanks well. $heck for toxic vapours prior to entering. Safety precautions etc/ @se oilskin3type protective suit with long rubber boots, gloves, safety goggles and helmet. =ave breathing apparatus available for immediate use when handling cargo gear and when entering pump rooms. @nauthorised personnel should not be allowed on deck when cargo transfer is in progress. =ave an antidote for poisoning available, see +ppendix D, $hapter 44#, ref %7;&. Materials / Stainless steel tanks are to be preferred, Iinc silicate coated tanks may be accepted provided the product is free from water. Hpoxy coatings are normally considered non3resistant. +MM'8,+ S'0@.,'8S, +T@+'@S +MM'8,+,826 S'0@.,'8S +mmonia, phosphates and potassium in various aquaous solutions. .oxitv/ 0ow toxity, odour warns before danger. $argo handling o not place close to heated cargoes as ammonia in solution has a tendency to ::boil off5. Some of these cargoes, however, are to be heated moderately in order to avoid crystallisation. $heck that vapour lines and pres3vac valves do not get clogged. Materials / Mild steel, stainless steel, rubber coatings %chloroprene, neoprene& are resistant. Brassware may corrode very rapidly %inter cristalline corrosion&. Bronze may be slightly attacked. .ank cleaning .anks can be washed with cold seawater. +S2=+0., B,.@MH8 =eavy petroleum products occuring naturally and as byproducts from refineries.

Melting point 9" degr.3 *#" degr $. 0oading temperatures *#" degr.34"" degr. $, discharging temperatures sometimes slightly lower. $ertain qualities %blown bitumen& still higher shipping temperatures %47":$&. $ontamination / Some remains of heavy oils may be tolerated. 0ight products should not be permitted. .ank condition prior to loading/ .anks and cargo piping must be completely dry %if not, eruptions due to the hot liquid may occur&. =eating coils must be drained or blown free of any water prior to loading. .he tanks should be preheated prior to loading in order to reduce thermal stresses. $argo handling on board/ Asph#$t can only be carried in tanks specially adapted for this product %heated cargo piping and pumps, extra heating coil area, tank structure arranged to give reduced thermal stresses etc&. .here are additives available which can be added to the product, giving it a lower surface tension thus reducing the effects of eruption due to any entrapped water. .he high cargo temperature causes thermal stresses. water stresses. istribute the cargo evenly in order to reduce still

.ank cleaning 3/ .he tank walls can be sprayed with a cold asphalt solution %as used in roadworks& and afterwards the tanks can be washed out with hot water. +lternatively the tanks can be successively upgraded by means of heated cargoes. Materials/ +sphalt tanks are normally not painted. Farning/ most tank coatings are non3resistant to the temperatures in question. BH8IH8H .oxity/ .oxic after prolonged contact, see ref %*&, %!&, %*;&, %7;&. $ontamination / iscolouration from previous cargoes. Sulphur compounds, see below.

.ank condition prior to loading/ 8ormally only light products such as naphta, aromatics, gasolines are accepted as last products. ,f oils %light& were last carried the tanks may have to be cleaned using solvent cleaners added to the washing water. $leaning agent sprayed onto the tank wails and with subsequent water washing or the floatation method using toluene could be used, see $hapter D. +fter completed discharge the tank must be properly ventilated prior to entering. Benzene vapours may be liberated from sediments, when draining valve bodies etc. $heck the atmosphere with toximeters, see $hapter ;. Materials / @ncoated steel is usually accepted, but coated tanks are preferable. Iinc silicate coatings are normally resistant to benzene while epoxy coatings are normally non3resistant. 2henolic coatings are rated as resistant, check with the coating manufacturer. $ommon flange gaskets of asbestos A nitrile rubber are usually acceptable. Hxpansion glands in cargo piping and shaft glands conventional in cargo pumps may, after long use with benzene, have to be substituted with 2.(H %teflon& impregnated packings. B@.L0 +$H.+.H

.oxitv/ Moderate, see ref %*&, %!&, %*;&. .ank condition prior to loading / .anks must be absolutely dry and free from hydrocarbons. 0oose rust must be re moved. .he tank must be rinsed with fresh water and dried. e $argo handling / Butyl acetate may decompose and form, acetic acid. .he product then turns aggresive against steel and zinc silicate tank coatings %against which it otherwise is neutral&. .he degree of acidity should be documented %not below p= #, # for zinc silicate coatings&. ,nsert blind flanges against other cargoes and keep seawater away. Materials / Mild steel tanks and epoxy coated tanks are commonly used. Regarding zinc silicate coatings see above.

B@.L0 +0$'='0 83 %B@.+8'0& .oxity/ Moderate, see ref %*&, %!&, %*;&. $ontamination/ Sensitive to contamination from other cargoes. 0ast three cargoes carried should preferably have been solvent type products %aromatics, naphta, alcohols etc&. .ank condition prior to loading/ .anks must be dry and free from cargo residues. 0oose rust to be removed as it may contain cargo residues. .anks to be rinsed with fresh water $argo handling / ,nsert blind flanges against other products on board. 6eep seawater out. Materials / Mild steel tanks, epoxy or zinc silicate coated tanks are acceptable.

B@.L0 -0L$'0 .oxity/ Moderate, see ref %*&, %!&, %*;&. $ontamination 3 Sensitive to contamination from hydrocarbon products and chlorides %salt&. .ank condition prior to loading/ 0ast three cargoes should preferably have been ::solvents:: %aromatics, alcohols etc& .he tank should be dry and clean and finally rinsed with fresh water. 0oose rust shall be removed %particle contamination& $argo handlingW/ ,nsert blind flanges against other cargoes and keep seawater away. Materials / Mild steel, epoxy and zinc silicate coatings are acceptable.

$+RB'8 B0+$6 (HH S.'$6 %$B(S& Rawmaterial for the production of carbon black. + heavy oil. .oxitv/ 8il. $ontamination / Sodium %8a& is a contaminant %max # Q 4 ppm&. Sodium is a component in salt %8a$l&. #" 3 *"" * seawater mixed into * """ tonnes of carbon black feedstok, may give a serious contamination. .ank condition prior to loading/ .ank and piping to be drained free of seawater. + certain amount of rust and other hydrocarbons are usually accepted. $argo handling / .ransport temperature !" 3 #" degr $. Materials / +ll common tank materials and coatings are acceptable.

$+@S.,$ S' + %S' ,@M =L R'V, H& .oxity / Strongly aggresive to human tissue, see ref %,&, %!&, %*;&. $ontamination / $austic soda intended for paper manufacture is sensitive to iron contamination, particularly rust. + common limitation is max *" 3 4# ppm iron. (or the aluminium, industry the requirements are somewhat less stringent, but spotlessly clean tanks are required. ue to its high viscosity and high specific gravity the product is sensitive to particle contamination. +ny particles left will settle very slowly out of the product. .ank condition prior to loading/ .anks must be kept clean from any hydrocarbon residues and loose rust. Surface rust may be accepted for the aluminium industry but cellulose industry will require uncoated tanks to be thoroughly cleaned. $oated tanks are preferred. +nodes of magnesium, zinc or other light alloys removed or they will be corroded away. .ank cleaning / Fash ,with cold water, no cleaning agents are, required. ,n some cases the cargo may leave drops of mercury behind on the bottom of the tank. .hese should be removed as the, tend to initiate local pitting corrosion. $argo handling / $austic soda is strongly aggresive to human tissue and eyesight is at a risk if splashes occur. @se full protective suit, oilskin type, gloves, rubber boots, protective goggles and a helmet, when handling hoses, taking ullages, etc. $austic soda corrodes copper alloys, however, not stronger than that various bronze fittings in pumps, valves etc can be accepted. $heck the condition of these details after a longer period in service. (or single voyages heating. coils of bronze alloys may be accepted. $ommon shipping concentrations are !9 3 #" < 8a '=. $orresponding lowest pumping temperatures are about 4" 3 44 degr. $. .his means that heating must normally be applied. ,n case of a break down of the

heating system the receiver may accept that the cargo be heated by introduction of live steam at the bottom of the tank. .he specific gravity of caustic soda is high %around *, !&. .his means that cargo tanks have to be strengthened above ::tanker for oil::3standards or special loading conditions discussed with the classification society in question. Materials / $austic soda destroys zinc silicate coatings. Hpoxy coatings are normally resistent, check with the manufacturer. ,n some cases time limitations for exposure to caustic soda are applicable. Stainless steel tanks/ no restrictions. $hloroprene %8eoprene& rubber is resistant to caustic soda. +ll common types of flange gaskets can be used. Hxpansion glands in cargo piping may have a tendency to leak after a period of time in caustic soda service. Fhite asbestos impregnated with 2.(H %.eflon& is suitable for repacking. $HRH$=0'R %trade name&

+ chlorinated hydrocarbon. .oxity / Moderate. $ontamination / $erechlor has a tendency to pick up zinc, tin, copper and also iron from uncoated tank surfaces. eteriorates with excess temperature. .ank condition prior to loading/ 8ormally coated tanks are required. .anks to be clean and dry. =eating coils of stainless steel %or possibly coated&. $argo handling / 2roduct to be kept at 4" 3 7" degr. $. Surface temperature of heating coils must not exceed 7#3!" degr. $. =eating system should preferably be circulating warm water or warm thermal oil. $argo can with advantage be recirculated periodically 0owest pumping temperature 4" degr. $. Materials / Hpoxy coating preferred. Iinc silicate coating may be acceptable for a product which is water3free and non3acidous $RHS'0 .oxity/ .oxic, see ref %*&, %!&, %*;&. $ontamination/ $resol is discoloured by light. .ank condition prior to loading/ .anks to be clean and dry and free from loose rust $argo handling / =eating to 7# 3 !" " $. +void over3temperature on the heating coils. =ot water circulation in the coils is preferred.

Material / .anks of mild steel are usually accepted. Hpoxy tank coatings non3resistant, zinc silicate coatings are usually acceptable., $L$0'3=HV+,8H $ontamination / iscolouration due to light. 2revious cargo remains.

.ank condition prior to loading / .anks to be clean and dry and free from rust. $argo handling / $yclo3hexane is particularly sensitive to the build3up of electrostatic charges. 0oading rate max * mAs until liquid covers filling pipe ends. Material / Mild steel tanks usually accepted. Hpoxy and zinc silicate coatings are usually acceptable. :: H.HR-H8.S:: Surface3active compounds, pure or mixed with water. .oxity/ -enerally low toxity. ,n some cases alkaline ad;ecl which may give some contact danger similar to caustic soda solutions. $ontamination/ .hese products are contaminated by the addition of water, salt and hydrocarbons. .hey may be damaged %oxidize& if sub1ected to heat and air for a longer period of time. +void temperatures above ;" " $. .ank condition prior to loading / .ank to be dry and free from the above contaminants. 2roper cleaning is required as the product will dissolve any cargo remains. .ank cleaning to finish with a fresh water rinse. $argo handling / .hese products have a tendency to foam during loading. 0oad at a low rate until the bottom suctions are well submerged. See to it that air does not enter throught pump shaft glands, valve spindles etc as foam, problems may then arise. =eating of the product and seawater contamination rnust be avoided. .ank cleaning./ .he products are water3soluble. ,n some cases slightly warmed water may be required to avoid gel formation. .he tanks can be washed with sea3water . (oaming may occur and may be reduced by the addition of some iso3butanol. (inally the tanks must be steamed and ventilated. Materials / Mild steel is usually accepted as tank material for detergents free of water. 2roducts with water contents are preferably shipped in stainless steel tanks. Resistance of tank coatings/ $heck with the maker of coating. (lange gaskets of rubber3asbestos type are generally resistant.

H.=L0 +$H.+.H .oxity / Moderate, see ref %*&, %!&, %*;&. $ontamination/ .his product is very sensitive tu nation from other products. +s last three cargoes tank aromatics, alcohols etc %solvents& should preferably have been carried. .ank condition prior to loading/ .anks having been rinsed with water must then be completely dry and free from previous cargoes and loose rust. $argo handling / Be aware of low/ flash point %3 # degr. $&.,nsert blind flanges against other cargoes. 6eep seawater out Materials / Mild steel tanks, epoxy coated , and zinc silicate %water free cargo& coated tanks are acceptable.

H.=L0 -0L$'0 .oxity Moderate, see ref %*&. %!&, %*;&. $ontamination/ .he product is very sensitive %/ to contamination from previous cargoes. +lso sensitive to odours remaining in the tank. .he last three cargoes should preferably have been very light products such as naphta, aromatics, alcohols etc. $hlorides %salt& is a serious contaminant. Rust and other particles should be carefully removed from the tanks as they cannot be settled out of the product easily. .ank condition prior to loading / .he final rinsing to be done with fresh water. .anks are to be dry and free from any previous cargoes, odour, rust and any particles. $argo handling / ,nsert blind flanges against other products. 6eep seawater out. Materials / Mild steel tanks, epoxy coated and zinc silicate coated tanks are usually accepted.

H.=L0 -0L$'0 +$H.+.H .oxity/ Mode r rate, see ref %*&, %!&, %*;&. $ontamination/ .he product is sensitive to contamination from other cargoes. .he last three cargoes should preferably have been very light products such as naphta, aromatics, alcohols etc.%solvents&. .ank condition prior to loading/ (inal rinsing with fresh water. .anks to be dry and free from remains of previous cargoes. 0oose rust to be removed. $argo handling / ,nsert blind flanges against other cargoes. 6eep seawater away. Materials / Mild steel tanks are usually accepted. Hpoxy coatings are normally accepted but the coating manufacturer may impose a max time allowed for the product %e g 7" days&. Iinc silicate coatings will be attacked if water is present. $heck with the maker of the tank coatings.

43H.=L0 =0V',$ +$, $ontamination/ .he product is very sensitive to contamination from previous cargo residues. See also '$.+8'0.

-0L$'. S %-H8HR+0& .oxity/ Moderate to little, see ref %*&, %!&, %*;&. $ontamination / -lycols intended for cosmetic and pharmaceutical products are sensitive to odour contamination %from, previous cargoes such as methanol, molasses, from cleaning agents, from uncured tank coatings etc&. $hlorides are a serious contaminant in certain cases %pharmaceutical grade max * ppm&. =igh viscosity and high specific gravity of many glycols make them sensitive to particle contamination %e g rust&. 2articles will be slow in settling out in shore tanks. .ank condition prior to loading/ .anks to be finally rinsed with fresh water. .anks to be well swept free of any sand, rust etc. .anks and piping to be drained. Mild steel tanks are usually accepted for water3free glycols but coated tanks %well cured& are to be preferred. Remaining odours to be removed by steamig , ventilation or repeated washing. 'dour3removing aerosols usually have little effect as the odour originates from minute cargo remains on the tank walls. + loading inspector may make a chloride test on the tank walls, see $hapter 9. "9. + pre3test can with advantage be made by the personnel on board to prove that fresh water rinsing has been adequate. $argo handling / 6eep seawater out and insert blind flanges against other products. $ertain glycols require heating, e g poly3ethylene glycol to max !9 degr. $. Materials / Hpoxy and zinc silicate coatings are acceptable for glycols.

0+.HV %-H8HR+0 R@0HS ('R 8+.@R+0 +8 .oxity/ 0ittie.

SL8.=H.,$ 0+.HV&

$ontamination / 0atex is damaged %lumps formed& if it freezes below " degr. $ or is kept above 7# 3 !" " $ for any duration of time. Rust and unprotected steel may contaminate latex. 8atural latex has added approximately ", D < ammonia to reduce its tendency to coagulate. .herefore galvanized steel, copper, brass cannot be used as these metals will be readily attacked by ammonia, which may also contaminate the product. .ank condition prior to loading / Mild steel tanks %uncoated& must be coated with a paraffin wax %melting point above *!" degr.$&. .he tank must be dry during the process.

.he tanks must be clean but need not be dry upon loading. ,t is said that wet tank walls while loading reduces the tendency for skin adherance after discharge. Sometimes the tanks are required to be sterilised prior to loading if the state of their cleanliness is held in any doubt. $argo handling / +void heating the product from neighbouring tanks. 8atural latex with ammonia added excerts a relatively high vapour pressure. 2resA vac valves may have to be set at max permissible value %",43",4# atm O 4 3 4,# m water col. &. + higher pressure is sometimes demanded by the shipper %",7 3 ",7# atm& but the tanks should then have been designed for such a pressure. +void unnecessary access of air to the tanks. .ank cleaning after discharge/ Fash with cold ,water immediately after discharge. +ny remaining skin on walls may then have to be peeled off manually. Be careful not to damage tank coatings Materials / Stainless steel tanks to be preferred. Mild steel tanks to be treated as, described above. Hpoxy coatings normally considered non3resistant. Iinc silicate and phenolic coatings have limited resistance/ check with the coating manufacturers. Most gasket materials are acceptable, incl rubber, 2umps/ 'rdinary pump shaft glands have a tendency to score in latex service %latex coagulates in contact with air&. ouble glands or double mechanical seals are advisable, as the intermediate medium, MH.=+8'0 %MH.=L0 +0$'='0& .oxity/ .oxic, see ref %*&, %!&, %*;&. $ontamination / Methanol is being contaminated by minor amounts of hydrocarbons %also light products& and by very small amounts of chlorides %salt&. Magnesium %a constituent in protective tank anodes& will form magnesium methylate which is a serious contaminant. .ank condition prior to loading/ .anks to be dry and absolutely free of any hydrocarbons. 0ast cargo preferably to have been a light product. 8o anodes in the tank. 0oose rust to be removed as it may contain traces of previous cargoes. 0ast rinsing to be done with fresh water. + tank inspector may make a chloride test, see $hapter 9."9 and a hydrocarbon test, see $hapter 9. "D, on the tank surfaces. ,n certain cases a permanganate time test is required, see ! $hapter 9. *;. Remember to conserve loading samples, on the 1etty, for reference. $ontamination may have occured before the product was loaded on board. $argo handling / o not locate near heated cargoes %to reduce evaporation losses&.

$hlorides contamination has occurred due to seawater ingress during voyage. 6eep tank lids carefully closed all 2res A vac valves protected from the possibility of water entering in bad weather.

Blank off heating coils.

8'8L0 2=H8'0 $ontamination/ +ir may cause a discolouration. $argo handling / ,nert gas %preferably nitrogen& blanketing during voyage. .he cargo tanks to be purged, if possible, with inert gas prior to loading.

'$.+8'0 %'$.L0 +0$'='0& .oxity / Moderate, see ref %*&, %!&, %*;&. $ontamination / Sensitive to contamination from previous cargoes. .he last three cargoes should preferably have been aromatics, alcohols etc. .ank condition prior to loading/ .anks to be finally rinsed with fresh water. .anks to be clean and dry and loose rust removed. Materials/ Mild steel tanks, epoxy and zinc silicate coated tanks acceptable. 2+R+3VL0H8H .oxity/ Moderate, see ref %*&, %!&, %*;&. $ontamination / Sensitive to contamination from previous cargoes. 0ast cargo should have been 5solvent:: like a*cc.hol, aromatics etc. 8ot acceptable last cargoes are vinyl acetate, styrene monomer, vegetable oils or animal oils, gasolines or products with anti3oxidation additives. .ank condition prior to loading/ .anks to be clean and dry and free from loose rust. >ery careful cleaning necessary, see $hapter D. $argo handling/ 2ara3xylene has a very high freezing point, R*7 degr. $. .he cargo should be kept around 4"37" degr. $. (reezing will occur from the sides and bottom of the tanks. .he botton, suctions may freeze and get blocked. Fith the shipper:s consent one may, if difficulties arise, 5lift:: the cargo onto a water bed in order to avoid blocking the tank suctions. Materials / Iinc silicate coatings are resistant to paraxylene. Hpoxy coatings are normally considered non3resistant. $heck with the maker. ,n any case epoxy coatings have to be very well cured. Hpoxy tar coatings 3are not acceptable as they may bleed and discolour the product.

Stainless steel/ no restrictions. $ommon flange gaskets of asbestos A rubber type are normaily resistant. $ommon packing in spindle glands and pipe expansion boxes may after some time have to be repacked with 2.(H3impregnated asbestos. 2=H,8'0 .oxity / >ery toxic, in particular to skin contact, see ref %*&, %!&, %*;&. $ontamination / 2henol may become discoloured by the effect of light, excess heating, minor amounts of alkaline matter, iron, copper, bronze and oxidation. .ank condition prior to loading/ 8ormally stainless steel tanks are to be preferred. Mild steel tanks can be accepted if a certain discolouration can be tolerated. .anks to be clean and dry and free from any alkaline matter %e g from last tank cleaning operation&. $argo handling / 2henol shall be kept at a temperature of min #" degr. $, max #93;" degr. $. Steam heating should be avoided/ overheating of the coils may result in discolouration and cargo claims. =eating should preferably be achieved by means of circulating warm water or by a heating oil in the coils thereby obtaining a better temperature regulation. 2henol vapours may sublime and form deposits on cold surfaces above the liquid level. Sometimes there are available special means of heating presAvac valves and vapour outlets in order to avoid the risk of blocking the same. =owever, in most cases of common exterior temperatures such heating may not be necessary. 6eep water away in order to avoid contamination. .ank gauging should be carried out by means of enclosed sounding devices in order to eliminate the risk of skin contact. .ank atmosphere / .he free exposure of the product to air should preferably be restricted. +void slack tanks. Sometimes inert gas blanketing is required above the cargo or driers inserted into the vacuum vents. Safety procedure/ @se an oilskin3type protective suit with long rubber boots, gloves, safety goggles and a helmet. =ave a breathing apparatus available and use it when entering the pump room and when handling cargo gear. 6eep unauthorised persons away? .ank cleaningW/ Fash the tanks with hot water and steam afterwards if necessary to remove any odour. Sometimes soda is added in the steam in order to achieve a degree of neutralisation. Materials / 8ormally stainless steel tanks are required by the shipper. Hpoxy and zinc silicate coatings are normally not guaranteed for use with phenol. -askets preferably of asbestos,A2.(H %.eflon& type or silicone type preferred. 2ump shaft seals preferably of a mechanical seal type. 2='S2='R,$ +$, %'R.'3& %#! <&

.oxitv/ Moderate, avoid splashes in the eyes. See ref %*&, %!&, %*;&. $ontamination / $hlorides %seawater, salt& is a serious contaminant %may cause corrosion to stainless steel&. Max permissible chlorides contents %as $l& are usually *""34"" ppm. Hven minor amounts of salt remaining on a stainless steel tank wall after cleaning may, in combination with acid remains, cause pitting corrosion. 6eep seawater and marine atmosphere away from stainless steel tanks ? .ank condition prior to loading / .anks to be free of previous cargoes. .anks to have been finally rinsed with fresh water. .anks need not necessarily be dry but no traces of seawater can be accepted. Stainless steel tanks should be free of any solid matter, rust flakes etc, or ob1ects under which crevice corrosion may occur. ,nspect the tanks closely before and after loadingAdischarge and note, or repair by grinding or welding, any corrosion attack from previous cargo. .ank cleaning %specifically stainless steel tanks&. .ank cleaning after phosphoric acid should preferably be carried out by the use of fresh water, but in any case the washing should end with a thorough fresh water rinse. 8o cleaning agents needed. 2roblems may be met in sediments accumulated on the tank floor. .hey can usually be washed out by manual hosing. +fter agreement with the receiver fresh water sediment washings :may be allowed to be discharged into the cargo shore tanks %provided the dilution effect is considered acceptable&. 2ersonnel entering an un3cleaned tank should wear a protective suit and a breathing mask. Sediments are in some instances washed out by means of recirculated phosphoric acid taken from the discharge stream. .he fresh water used for washing purposes may be slightiy alkaline by the addition of soda %neutralises acid remains and reduces corrosion in the fresh water tanks when evaporated water is being used&. $argo handling / 2rior to loading/ check the specification of the cargo to be loaded against charter party or contract, with particular regard to the chloride contents, fluorides and the contents of sediments. ,f the cargo temperature is high %say !"3#" degr. $& one should be careful not to accept excessive contents of chlorides %and fluorides&. =igh contents of iron and aluminium counteract to a certain degree the corrosiveness due to excessive chlorides. $ommercial phosphoric acid contains particles of gypsum and various phosphates in suspension. .his matter has a tendency to settle out on the tank bottom as a clay3like sediment, sometimes in considerable amounts. + drop in temperature during the voyage will accelerate the fall3out of sediments. Similarly newly produced acid will have a higher fall3out rate. Some ships have circulation systems whereby the acid can be held in movement with much less fall3out as a result. Spillage of acid in pump rooms may cause corrosion problems, 2ump room bottoms may be epoxy coated as a protection and pumps provided with drip pans. Fash out pump room bilgesE some soda solution may be added to neutralise any spilt acid. Materials / Stainless steel of high molybdeniurn3low carbon %max ", "# <& are normally resistant to phosphoric acid provided chlorides contents and temperatures are within normal specifications, see above. $ommon types are +,S, 7*; 0, +,S, 7*D *3, S,S 47#73

Rubber lined tanks are common ashore and are also used on some ships. $hloroprene %8eoprene& is then suitable as it is durable against sun radiation, ozone and accidental spills of oil. 8atural rubber is frequently used in tanks ashore. -askets of 2.(HAblue asbestos, envelope 2.(H, rubber,: asbestos and rubber can be used. S.LRH8H M'8'MHR .oxity/ Moderately toxic, see ref %*&, %!&, %*;&. $ontamination / Styrene polymerises under the influence of light, oxygen, heat, rust etc, 2olymerisation can be observed as a discolouration and also as deposits on tank surfaces. $opper with alloys may also cause discolouration. .ank condition prior to loading/ .anks must be dry and clean and free from all loose rust. =eating coils must be blind flanged. ,nsert blind flanges against other cargoes. $argo handling 3 Maximum transport temperature 74 " $ Styrene must not be placed in bulkhead contact with heated cargoes. $ool the deck by hosing seawater over it on very hot days Styrene has an inhibitor added against polymerisation. .he inhibitor, being consumed with time, may fall out in cases of low temperatures. +dding inhibitor is a 1ob for specialists. .he inhibitor is usually tert butyl catechol %.B$& which is added to a concentration of ca *# ppm. .he contents should not be permitted to go below 9 ppm. + check on contents of the inhibitor can be made by means of a colour comparison and a reference scale. + check on the amount of polymerisation can be made by mixing * part of styrene with 7 parts of methanol. ,f the mixture remains a clear liquid or shows an only slightly bluish shadow, the product is probably intact. 2olymerisation can be observed as a whitish shadow. .he shipper sometimes requires styrene monomer to be transported with inert gas blanketing. .ank cleaning. .anks must be washed immediately after discharge with cold water. ,f washing cannot be carried out it is adviseable to keep the tank filled with cold water until washing can take place. Sometimes polymerised material has to be removed manually. ,n the final cleaning detergents or solvent cleaners must be used. (inal steaming may be necessary to remove remaining odours. $hlorethane can be used for cleaning valves, glands etc. emand a certificate of inhibition from the shipper? S@02=@R,$ +$, , $'8$ .oxity/ Strongly aggressive to human tissue. See ref %*&, %!&, %*;&. .ank condition prior to loading / .anks dry and clean. $argo piping drained free of 3water.

$argo handling / @se full protective suit %oilskin type&, gloves, long rubber boots, protective goggles and a helmet, when handling hoses, taking ullages etc. Sulphuric acid may react violently to a number of products %e g water, caustics, some polymerisable products& see data in ref %*& and +ppendix 7. Sulphuric acid must not be placed with bulkhead contact to such cargoes or in tanks being part of the side shell or bordering filled ballast water tanks. 8ever introduce water into sulphuric acid? +n eruption of acid may follow. $onc sulphuric acid %above approx G!3G; <& does not attack steel. iluted acid is strongly corrosive to mild steel and also to stainless steels. (ill the cargo tanks as much as expansion margin permits. Moisture in the air may cause diluted acid on the tank walls with corrosion as a consequence. 6eep pump room bottoms free from acid spills. =ose down and drain any acidous bilge water. +dd some alkaline water %soda added& to the bilges, this will reduce corrosion. 0itmus paper can be used as a check on acidity of the bilges. .ank cleaningW/ +fter discharge the tank bottoms and piping should be filled with water immediately and the whole tank thoroughly washed with cold water. ,t is a question of rapidly reducing the acid concentration to harmlessly low values. + final rinsing with alkaline %with soda added& water is advantageous. Materials/ Mild steel and stainless steels are resistant to conc sulphuric acid %G! 3G# <& +t the moment there are no tank coatings available which are resistant to sulphuric acid . (lange gaskets of asbestosArubber type are acceptable. +sbestosA 2.(H %.eflon& gaskets or envelop 2.(H3gaskets are preferable. .'0@H8H, VL0H8H .oxitv / Moderate, see ref %*&, %!&, %*; $ontamination / iscolouration from previous cargoes. Vylene ::nitration grade:: is sensitive to contamination by chlorides %salt&. .ank condition prior to loading/ 0oose rust should be removed as it may contain residues of previous cargoes. Rust in itself is acceptable. Before xylene ::nitration grade:: the tanks should be rinsed with fresh water. .he tank inspector may make a ::presence of hydrocarbon test5, see $hapter 9. ";, 9. "D, 9. "9. ,n case of doubt the ship:s officers can make these tests themselves before hand. .o obtain the necessary degree of cleanliness methods outlined in D. "!!, floatation, may have to be used. $argo handling / ,n order to avoid cargo evaporation losses these products should not be placed close to heated cargoes. Blank off heating coils.

Materials / Iinc silicate coatings are resistant to toluene and xylene. Hpoxy coatings are normally considered non3resistant or have time limitations, check with the coating manufacturer. ,n any case epoxy coatings must be very well cured and aged. Hpoxy tar coatings are non3resistant and may discolour the cargoes. Stainless steel tanks/ no restrictions. $ommon flange gaskets of asbestosArubber type can be considered resistant. Hxpansion glands in cargo piping, spindle boxes etc may have to be repacked with 2.(H impregnated asbestos after some time in service.

>H-H.+B0H ',0S ata/ See ref %*&. +s examples can be mentioned/ Solidifying temp degr. $ $ottonseed oil -roundnut oil $apok seed oil $oconu oil 0inseed oil 'live oil 2alm oil 2alm kernel oil Soya bean oil Sunflower seed oil .ung oil %$hinese wood oil& * 3*" **,# *# 3 4* 3 9 C 3 *# 4! 3 !" 4; 3 7" 3 9 C 3 *# 7 4" 3 49 Melting temp degr. $

44 3 7* 7*

Specific gravities in the range ", G*3",G#. .oxitv/ .hese products are non3toxic. .here have been accidents, however, when tanks have been entered 1ust after completed discharge. .here are indictions that the lack of oxygen may have been the cause. 'xidising oils may be more dangerous in this respect. >entilate well? $ontamination/ 'dour and remains from previous cargoes may be a serious contaminant. Strongly smelling products %methanol, octanol, molasses etc& rnay lessen the value of edible products considerably. iscolouration may result due to overheating from heating coils with a too high surface temperature. >egetable oils may be contaminated and become toxic if the are carried in zinc silicate coated tanks under incorrect conditions %see below&.

>egetable oils may increase their contents of free fatty acids abnormally and turn rancid if/ 3 .he tanks are poorly cleaned from previous cargoes %bacteria from vegetable or animal oils& 3 .he cargo is carried at an unnecessarily high temperature 3 .he ullage space %air& is unnecessarily large 3 Sun radiation, light or heat is applied onto the cargo. .ank condition prior to loading/ 8ormally vegetable oils are carried in coated tanks. @ncoated mild steel tanks must be free from rust. ,n order to remove odours the tanks may have to be steamed. $leaning by means of soda or any other cleaning agents is normally required. (inally a fresh water rinse. Manual cleaning may be necessary in awkward corners etc. .ank inspectors will scrutinise very carefully? $apok seed oil in particular requires well cleaned tanks. =eating coils to be tested prior to loading. ,ndependent surveyors are usually called in to certify tank cleanliness. ,n some cases tightness tests are required. .hey are often carried out with air at about ", * kpAcm P4 %* m water head& with tank boundaries etc tested with soap water. $argo handling / ,nsert blind flanges against cargoes of a different nature. 8ever load vegetable oils ad1acent to toxic cargoes ? ,nsert blind flanges, which are necessary for separation? =eat the cargo according to instructions from the shipper. =eat with great caution in order not to burn the cargo, in particular soya bean oil, cottonseed oil, capok seed oil, linseed oil, tung oil. +d1ust the admission of steam, not to return condensate ? o not heat more than instructed. ,n certain cases one voyage temperature and another discharge temperature is stipulated %e g capok seed oil/ voyage **3*7 degr. $, discharge 4!37" degr. $&. ,ncrease heating very slowly? uring the voyage there will, usually and normally, be an increase in the amount of free fatty acids %((+&. 2rior to loading the amount of ((+ should be determined by an independent surveyor and the result documented. .he vessel may be held responsible for an abnormal increase in ((+3contents. .he increase3 in ((+ will be greater, the higher ((+3contents there are at the beginning. .he following vegetable oils normally require heating/ cottonseed oil, coconut oil, palm oil, palm kernel cii. 'ther vegetable oils may require heating at low ambient temperatures. .ank cleaning after vegetable oils 3/ See also $hapter D. ,t is important that cleaning is commenced immediated .0 after discharge. ,f the tank is filled with ballast water for a period of time the cleaning may become much more difficult. 'bserve the cleaning routine for drying oils/ Start the cleaning with cold water %e g castor seed oil, cotton seed oil, linseed oil, ground nut oil, tung oil, soya bean oil and sunflower oil&. Materials / Hpoxy tank coatings generally have a good resistance against vegetable oils. Iinc silicate coatings may be affected by the cargo and the cargo suffer a zinc pick up if vegetable oils have a too high contents of free fatty acids.

@suallv 4, # < of free fatty acids are tolerated, for short voyages up to # <. 2alm oils and coconut oils should not be carried in zinc silicate coated tanks. .he 8igerian 2roduce Marketing Board gives the following general guidance for the carriage of vegetable oils %((+ means free fatty acids&/ =H+.,8- ,8S.R@$.,'8S ('R 2+0M ',0 *& Ship:s coils must be completely covered by the oil on completion of loading. 4& 8o heat shall be applied until the average temperature of the oil has fallen till G# " (. for oil up to and including ;< ((+ and *"# degr.( for oil exceeding ;* < ((+. =eat should then be applied to maintain these temperatures until the sixth day prior to arrival at port of discharge. 7& +s from the sixth day prior to arrival at port of discharge, temperature should :be raised steadily %not more than # degr. ( in 4! hours& in order to reach but not exceed the following average temperatures on discharge/ *4# degr. ( for oils up to and including ;*< ((+ and *7# degr.( for oils exceeding ;* < ((+ on shipment. !& uring the winter months, namely from 8ovember to +pril inclusive the foregoing temperatures my be increased by # degr.(. #& .op and bottorn ternperatures should be maintained as equal as possible. ;& S2H$,+0 F+R.8,8- 3 + sudden increase in temperature must be avoided as it will almost certainly result in damage to the oil. D& .hese instructions may be varied only by official wireless or written notification. amendment3s and the authority responsible must be duly recorded. etails of any

9& +t the time of loading the correct and true ((+ of the oil loaded must be stated on the loading and carriage log.

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E+#erpt .romB IMC( B C Co e .or t,e Constru#tion an 2ul" EDuipment o. S,ip5s Carrying 3angerous C,emi#,als in

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E+erpt .rom B ME3ICAL &IRST AI3 08I3E &(R 8SE I) ACCI3E)TS I)A(LAI)0 3A)0ER(8S 0((3S

"eprinted #y the permission of the nter $ %o&ernmental 'aritime Consultati&e (rgani)ation