Transport of Liquid Chemicals in Bulk

Transcription

1 1 Transport of Liquid hemicals in Bulk Safety azards Precautions onstruction of the vessel Arrangement and Equipment Whenever a transport of liquid chemicals in bulk has to be undertaken in a safe manner, it is of utmost importance to be aware of the dangers that might arise from such a transport. Furthermore it is essential to know which precautions should be taken to avoid or eliminate the hazards and to be familiar with all contingency plans. The most predominant hazards in a chemical tanker are: Toxicity Fire and explosions orrosion Pollution To protect the crew, the vessel, the cargo and the environment precautions may be implemented in the following fields onstruction of the ship Arrangement and equipment of the ship The behaviour and education of the crew. Besides the usual requirements as to stability, strength etc. more specific and elaborate requirements are given for chemical tankers. These requirements are established by the IMO in the IB-code (International ode for the onstruction and Equipment of Ships carrying dangerous hemicals in Bulk) and are endorsed by national authorities such as the Danish Maritime Authority "Søfartsstyrelsen" and by the classification societies. Of course ship arrangements and equipment must be in accordance with regulations from national authorities, but again the IMO has established fundamental rules depending on which products the vessel is intended to carry Behaviour of the crew Neither the construction nor the equipment of a vessel can eliminate all dangers which may arise from the cargo. If the crew does not behave in a safe manner, all technical safety efforts will be in vain. It is therefore of utmost importance that everyone on board knows the hazards and knows how to avoid them. Furthermore, it must be strongly emphasised that a violation of the safety rules causes danger, not only to the man violating the rules but to the whole crew and the environment. The crew of a chemical tanker must be utterly competent. Besides the knowledge of the inherent dangers of the products they must be

2 2 familiar with internal ompany regulations as well as Port State regulations and Flag State regulations. All aboard should be familiar with such rules, not just some key personnel. In 1978 the IMO called for a conference on education of seafarers. The conference adopted a convention commonly known as the STW-convention (Standards of Training, ertification and Watchkeeping for Seafarers, 1978). The text of the convention has been changed several times and the current regulations regarding chemical tankers are found in Regulation V/1-1 and in STW ode section A-V/1-1. This course has been compiled in accordance with the STW onventian and ode, including 2010 Manila Amendments. The 2010 amendments Special requirements for tankers onvention on Standards of Training, ertification and Watchkeeping for Seafarers (STW), 1978 The STW onvention has been recognised by almost all seafaring nations and that is 158 nations representing almost 99% of the world tonnage (May 2014). Section A-V/1-1, Table A-V/1-1-3 and section B-V/1-1 in the STW ode give description and guidance on the training programme for the advanced training for chemical tanker cargo operations. hapter V in the onvention deals with Special training requirements for personnel on certain types of ships. The importance of tankers in world shipping is recognized by the inclusion of this chapter. Its intention is to ensure that officers and ratings who are to have specific duties related to the cargo and cargo equipment of tankers shall have completed an approved basic safety training (STW A-VI/1) and have completed either an approved period of seagoing service on oil or chemical tankers, or an approved basic training for oil and chemical tankers. Requirements are more stringent for masters and senior officers. Attention is paid not only to safety aspects but also to pollution prevention. The chapter contains two regulations dealing with oil tankers and chemical tankers - and liquefied gas tankers, respectively. hapter V is shown on the following two pages:

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5 5 For Danish ships, order no of 21 October 2013 is in force: Uddrag af Søfartsstyrelsens bekendtgørelse nr af 21. oktober 2013 Bekendtgørelse om kvalifikationskrav til søfarende og fiskere og om sønærings- og kvalifikationsbeviser I medfør af 18, 19, stk. 1, 20, 25 b, stk. 1 og 2, og 27, stk. 3, i lov om skibes besætning, jf. lovbekendtgørelse nr. 168 af 27. februar 2012, som ændret ved lov nr. 493 af 12. maj 2010, lov nr af 18. december 2012 og lov nr af 23. december 2012, fastsættes: Kvalifikationskrav til personel og beviser for tjeneste i tankskibe Om tjeneste i tankskibe 35. Officerer, befarent skibsmandskab og enhver anden person, som i forbindelse med ladning og lastbehandlingsudstyr har særlige opgaver og særligt ansvar i tilknytning til disse, skal være i besiddelse af bevis for gennemført godkendt kursus om grundlæggende tankskibsoperationer for olie-, kemikalie- og gastankskibe, jf. STW-konventionens reglement V/1-1, paragraf 2.2, og reglement V/1-2, paragraf 2.2. Stk. 2. Skibsførere, overstyrmænd, maskinchefer, 1. maskinmestre, duale seniorofficerer og enhver anden person, der under tjeneste har direkte ansvar for lastning, losning og kontrol med ladningen under rejsen eller for arbejde med ladningen, skal ud over opfyldelse af kravene i stk. 1 være i besiddelse af et gyldigt kvalifikationsbevis for ledelse af operationer for den type tankskib, der gøres tjeneste på. Stk. 3. I stedet for det i stk. 1 omhandlede bevis kan Søfartsstyrelsen tillade, at befarent skibsmandskab i skibe registreret i Dansk Internationalt Skibsregister har erhvervet udenlandsk bevis udfærdiget i henhold til bestemmelserne i STW-konventionens reglement V/1-1, paragraf 2.2, og reglement V/1-2, paragraf 2.2. Stk. 4. Sønæringsbeviser til duale skibsofficerer, navigations- og maskinofficerer indeholder det i stk. 1 omhandlede bevis. Om kvalifikationsbeviser for tjeneste i tankskibe 36. Til erhvervelse af kvalifikationsbevis for ledelse af operationer for olie-, kemikalieog/eller gastankskibe kræves, at vedkommende 1) har gyldigt sønæringsbevis, der giver ret til tjeneste som dual skibsofficer, navigatør eller maskinmester, 2) har forrettet tjeneste i 3 måneder som officer i den type tankskib, hvortil beviset er gyldigt, eller har forrettet tjeneste i mindst 1 måned som overtallig officer i den type tankskib, hvortil beviset er gyldigt, og under tjenesten dokumenterer mindst 3 lasteoperationer og 3 losseoperationer og 3) har gennemført et godkendt kursus for ledelse af operationer for henholdsvis olietankskib (STW-reglement V/1-1, paragraf 3), kemikalietankskib (STW-reglement V/1-1, paragraf 5) eller gastankskib (STW-reglement V/1-2, paragraf 3), hvortil beviset er gyldigt. Fornyelse af sønæringsbeviser og kvalifikationsbeviser 63. For fornyelse af et sønæringsbevis som dæks- eller maskinofficer eller for fornyelse af et tankskibsbevis for officerer kræves det, at vedkommende er i besiddelse af sundhedsbevis, der er gyldigt for den tjeneste, som beviset giver ret til, og dokumenterer at

6 6 have gjort godkendt tjeneste i søgående skibe som henholdsvis navigatør, dual skibsofficer eller maskinmester i mindst 1) 1 år inden for de forudgående 5 år eller 2) 3 måneder inden for de sidste 6 måneder forinden fornyelse af beviset. Stk. 2. For fornyelse af et sønæringsbevis som dæks- eller maskinofficer med gyldighed efter 31. december 2016 skal vedkommende ud over de i stk. 1 nævnte krav dokumentere at have vedligeholdt kvalifikationer om grundlæggende søsikkerhed og om brandbekæmpelse i skibe for skibsofficerer. Stk. 3. For fornyelse af et tankskibsbevis på ledelsesniveau kræves det, at vedkommende er i besiddelse af et sundhedsbevis, der er gyldigt for den tjeneste, som beviset giver ret til, og dokumenterer at have gjort godkendt tjeneste i søgående tankskibe af den type, som beviset giver ret til, i mindst 3 måneder inden for de forudgående 5 år. Stk. 4. Anerkendelse af tjeneste som dual skibsofficer i henhold til stk. 1 forudsætter, at vedkommende har virket i en stilling som dual skibsofficer i henhold til en besætningsfastsættelse. vis personen har indgået i en sådan stilling, har vedkommende optjent fartstid som både navigatør og maskinmester. Stk. 5. vis et sønæringsbevis som dæks- eller maskinofficer eller et tankskibsbevis på ledelsesniveau er udløbet, kan fornyelse ske for personer, der har gennemført et kursus i søsikkerhed og brandbekæmpelse for skibsofficerer og 1) har bestået en prøve, hvis indhold og omfang fastsættes af Søfartsstyrelsen under hensyn til den pågældendes eksamensår, fartstid, dokumenteret praktisk erfaring og sidste udmønstring, og med tilfredsstillende resultat har gennemgået et eller flere kurser efter Søfartsstyrelsens bestemmelser eller 2) dokumenterer at have gjort tjeneste i søgående skibe i mindst 3 måneder umiddelbart forinden fornyelse af beviset som navigatør, maskinmester eller dual skibsofficer i overtallig stilling eller maskinmester i lavere stilling end den, der svarer til pågældendes bevis. Stk. 6. Ud over bestemmelserne i stk. 5 skal en person med sønæringsbevis som navigatør udstedt før 1. februar 1997 have gennemført supplerende uddannelses- og/eller kursuskrav fastsat af Søfartsstyrelsen under hensyn til den pågældendes sønæringsbevis, som skal fornyes. Stk. 7. Fornyelse af et sønæringsbevis som dæksofficer i handelsskibe og for sønæringsbevis som styrmand af 3. grad i fiskeskibe eller højere kan kun ske, hvis den pågældende er i besiddelse af certifikat som radiooperatør i GMDSS (GO, LR eller RO). Stk. 8. Ud over bestemmelserne i stk. 1 skal en person med et gyldigt sønæringsbevis som navigatør eller maskinofficer udstedt før 31. december 2016 opfylde de særlige uddannelseskrav, der er fastsat i bekendtgørelsens bilag 2 for at kunne få udstedt et sønæringsbevis som dæks- eller maskinofficer med en gyldighed efter 31. december 2016 og med samme sønæringsrettigheder som det sønæringsbevis, som skal fornyes. Stk. 9. En person med et gyldigt sønæringsbevis som navigatør i fiskeskibe udstedt før 1. februar 1997 kan få udstedt et sønæringsbevis som navigatør i fiskeskibe påtegnet efter STW-F-konventionen med samme sønæringsrettigheder som det sønæringsbevis, som skal fornyes, når vedkommende 1) opfylder bestemmelserne i stk. 1 og 2) består prøver eller gennemfører kurser efter Søfartsstyrelsens bestemmelse under hensyntagen til den pågældendes eksamensår og senere beskæftigelse. Stk. 10. Søfartsstyrelsen udsteder fornødent sønæringsbevis som vagthavende maskinmester til personer, der udfører tjeneste som nævnt i stk. 5, nr. 1 litra b. Stk. 11. Fornyelsen af et sønærings- og kvalifikationsbevis kan tidligst ske 6 måneder inden udløb af et eksisterende sønærings- og kvalifikationsbevis.

7 7 Structure of IMO It will be appropriate briefly to introduce the structure of IMO as most rules and regulations met in the tanker business originate from IMO. The Organization consists of an Assembly, a ouncil and four main ommittees: the Maritime Safety ommittee (MS); the Marine Environment Protection ommittee (MEP); the Legal ommittee; and the Technical ooperation ommittee. There is also a Facilitation ommittee and a number of Sub-ommittees support the work of the main technical committees. The Assembly The ouncil This is the highest Governing Body of the Organization. It consists of all Member States (170 by May 2014) and it meets once every two years in regular sessions, but may also meet in an extraordinary session if necessary. The Assembly is responsible for approving the work programme, voting the budget and determining the financial arrangements of the Organization. The Assembly also elects the ouncil. The ouncil is elected by the Assembly for two-year terms beginning after each regular session of the Assembly. The ouncil is the Executive Organ of IMO and is responsible, under the Assembly, for supervising the work of the Organization. Between sessions of the Assembly the ouncil performs all the functions of the Assembly, except the function of making recommendations to Governments on maritime safety and pollution prevention which is reserved for the Assembly. Other functions of the ouncil are to: (a) co-ordinate the activities of the organs of the Organization; (b) consider the draft work programme and budget estimates of the Organization and submit them to the Assembly; (c) receive reports and proposals of the ommittees and other organs and submit them to the Assembly and Member States, with comments and recommendations as appropriate; (d) appoint the Secretary-General, subject to the approval of the Assembly; (e) enter into agreements or arrangements concerning the relationship of the Organization with other organizations, subject to approval by the Assembly.

8 8 ouncil members for period biennium. ategory (a): 10 States with the largest interest in providing international shipping services: hina Greece Italy Japan Norway Panama Republic of Korea Russian Federation United Kingdom United states ategory (b): 10 other States with the largest interest in international seaborne trade: Argentina Bangladesh Brazil anada France Germany India Netherlands Spain Sweden ategory (c): 20 States not elected under (a) or (b) above which have special interests in maritime transport or navigation, and whose election to the ouncil will ensure the representation of all major geographic areas of the world: Australia Bahamas Belgium hile yprus Denmark Indonesia Jamaica Kenya Liberia Malaysia Malta Mexico Morocco Peru Philippines Singapore South Africa Thailand Turkey Maritime Safety ommittee (MS) The MS is the highest technical body of the Organization. It consists of all Member States. The functions of the Maritime Safety ommittee are to consider any matter within the scope of the Organization concerned with aids to navigation, construction and equipment of vessels, manning from a safety standpoint, rules for the prevention of collisions, handling of dangerous cargoes, maritime safety procedures and requirements, hydrographic information, log-books and navigational records, marine casualty investigations, salvage and rescue and any other matters directly affecting maritime safety. The ommittee is also required to provide machinery for performing any duties assigned to it by the IMO onvention or any duty within its scope of work which may be assigned to it by or under any international instrument and accepted by the Organization. It also has the responsibility for considering and submitting recommendations and guidelines on safety for possible adoption by the Assembly.

9 9 The expanded MS adopts amendments to conventions such as SOLAS and includes all Member States as well as those countries which are Party to conventions such as SOLAS even if they are not IMO Member States. The Marine Environment Protection ommittee (MEP) Sub-ommittees The MEP, which consists of all Member States, is empowered to consider any matter within the scope of the Organization concerned with prevention and control of pollution from ships. In particular it is concerned with the adoption and amendment of conventions and other regulations and measures to ensure their enforcement. The MS and MEP are assisted in their work by seven sub-committees which are also open to all Member States. They deal with the following subjects: Sub-ommittee on uman Element, Training and Watchkeeping (TW); - former STW Sub-ommittee on Implementation of IMO Instruments (III); Sub-ommittee on Navigation, ommunications and Search and Rescue (NSR); Sub-ommittee on Pollution Prevention and Response (PPR); - former BLG Sub-ommittee on Ship Design and onstruction (SD); Sub-ommittee on Ship Systems and Equipment (SSE); and Sub-ommittee on arriage of argoes and ontainers (), former DS (The composition of the subcommittees was amended with effect from January The next page shows - for information the subcommittees as they were up till end of2013) ESP working group Under the subcommittee PPR (former BLG) a powerful working group has been established with the purpose of the Evaluation of Safety and Pollution azards.

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11 11 Types of tankers and the products they carry There are five main types of tankers: ombination Tankers, rude Oil Tankers, Product Tankers, hemical Tankers, and Liquefied Gas Tankers. It can, however be difficult to distinguish between the main types and a few tankers cannot be placed in the above division. ombination Tankers or OBO-carriers (oil/bulk/ore) are mainly large ships designed to carry bulk cargoes (coal, grain, ore), but they are also equipped for the carriage of crude oil, both in wing tanks and holds. Owing to the special risks of these ships they are subject to a special set of safety rules m 3 OBO arrier

12 12 rude Oil Tankers are ships which are designed to transport nothing but crude oil. Often they are very large with comparatively few cargo tanks. They have a simple piping system and very large cargo pumps in order to make a fast loading and discharging. A crude carrier of more than 200,000 TDW is often called a VL (Very Large rude arrier) and a tanker of more than 300,000 TDW is called a UL (Ultra Large rude arrier) TDW rude Oil arrier with Double ull Note: Oil tankers of more than TDW delivered before 6 July 1996 would most probably have been constructed with no double hull. MARPOL Annex I regulation 20 gives phase-out requirements to single hull oil tankers of more than TDW. The conclusion is - that such an oil tanker must either meet the requirements for a double hull tanker or be taken out of service as an oil tanker on the anniversary date of delivery in Product Tankers cover ships of all sizes and qualities. Ships for dirty petroleum products (DPP) are very like crude oil ships but smaller and they have equipment for heating of the cargo, which is often some quality of fuel oil. Tankers for clean petroleum products (PP) usually have many cargo tanks and a high developed piping system proportional to the size of the ships. This enables them to carry several products at the same time and to load and discharge without contamination among the various grades. lean oil ships are often so well equipped that they are certified to carry some solvents and less dangerous chemicals - and also vegoils.

13 TDW Product arrier As to safety and equipment all the above ships are subject to the rules and regulations of "Tanker for Oil". hemical Tankers are a further development of clean oil ships. They are seldom of more than 40,000 TDW and they often have a separate piping system for each cargo tank TDW hemical Tanker

14 TDW hemical Tanker As to construction, operation and crew, chemical tankers are subject to IMO's rules: "International ode for the onstruction and Equipment of Ships arrying Dangerous Substances in Bulk" (the IB-code). Liquefied Gas Tankers are a special variety of chemical tankers due to the products they carry. As to construction and equipment, however, they differ so much from other tankers that the IMO rules for chemical tankers cannot be used directly. But this fact does not prevent gas tankers from time to time to operate in the chemical trade. IMO has a special set of rules for gas tankers: "International ode for the onstruction and Equipment of Ships arrying Liquefied Gases in Bulk" (the IB-code). Gas tankers are mostly divided into four main types: 1: Fully pressurized ships 2: Fully refrigerated ships 3: Semi-pressurized/Fully refrigerated ships 4: Insulated ships 1: The product is carried under such a pressure that it will be a liquid at the ambient temperature i.e. pressure in the tank equals vapour pressure of product. System is mostly used for smaller tankers carrying propane/butane and ammonia. 2: The product is carried at a temperature close to the boiling point. The ship's compressors are able to extract the boil-off gas to maintain low temperature and even to cool-down the cargo if necessary. The boil-off gas is reliquefied in a condenser and carried

15 15 back to the tank. The method is used mostly in LPGships but also in some LNG-carriers. 3: In semi-pressurized ships the gas is liquefied partly by cooling and partly through pressure. The tanks are insulated and have fixed limits for pressure, temperature and density and this combination renders it possible to carry a wide range of products, even some chemicals. 4: On insulated ships you will find no reliquefaction plant. The product is delivered sub cooled and in liquid form by the shipper and rise in temperature is met with through boil-off. The system is suitable for large LNG-ships where the boil-off gas is used as fuel for propulsion of the ship m 3 Semi pressurized/fully refrigerated

16 m 3 Fully refrigerated Types of tanks In the transportation of gases the types of tanks are of great importance. IMO has laid down the following definitions. Integral tanks Independent tanks Membrane tanks Integral Tanks Independent Tanks form a structural part of the ship's hull and the "design vapour pressure" should normally not exceed 0,25 Bar. Integral tanks is only used for special products of which the temperature will not fall below -10. are self-supporting and do not form part of the ship's hull. Such tanks are often named according to shape and the construction of the tanks is dependent on maximum pressure and minimum temperature. The greater part of the worlds gas tanker fleet is fitted with independent tanks.

17 17 Membrane Tanks are non-self-supporting tanks which consist of a thin layer (membrane) supported through insulation by the adjacent hull structure. The membrane is designed in such a way that thermal expansion or contraction is compensated for without undue stressing of the membrane. Semi-membrane Tanks are membrane tanks with flat sides, bottom and top and rounded edges to compensate for thermal expansion or contraction. Independent tanks are named after their shape thus: Spherical Tanks ylindrical Tanks Prismatic Tanks

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19 19 IMO Regulations, IB-code There are several international regulations, which are important for chemical tankers. The most fundamental regulation is the SOLAS convention which defines and makes the IB-code mandatory. Extract from SOLAS chapter VII Part B onstruction and equipment of ships carrying dangerous liquid chemicals in bulk Regulation 8 Definitions For the purpose of this part, unless expressly provided otherwise: 1 International Bulk hemical ode (IB ode) means the International ode for the onstruction and Equipment of Ships arrying Dangerous hemicals in Bulk adopted by the Maritime Safety ommittee of the Organization by resolution MS.4(48), as may be amended by the Organization, provided that such amendments are adopted, brought into force and take effect in accordance with the provisions of article VIII of the present onvention concerning the amendment procedures applicable to the annex other than chapter I. 2 hemical tanker means a cargo ship constructed or adapted and used for the carriage in bulk of any liquid product listed in chapter 17 of the International Bulk hemical ode. 3 For the purpose of regulation 9, ship constructed means a ship the keel of which is laid or which is at a similar stage of construction. 4 At a similar state of construction means the state at which:.1 construction identifiable with a specific ship begins; and.2 assembly of that ship has commenced comprising at least 50 tonnes or 1 % of the estimated mass of all structural material, whichever is less. Regulation 9 Application to chemical tankers 1 Unless expressly provided otherwise, this part applies to chemical tankers constructed on or after 1 July 1986 including those of less than 500 tons gross tonnage. Such tankers shall comply with the requirements of this part in addition to any other applicable requirements of the present regulations. 2 Any chemical tanker, irrespective of the date of construction, which undergoes repairs, alterations, modifications and outfitting related thereto shall continue to comply with at least the requirements previously applicable to the ship. Such a ship, if constructed before 1 July 1986 shall, as a rule, comply with the requirements for a ship constructed on or after that date to at least the same extent as before undergoing such repairs, alterations, modifications or outfitting. Repairs, alterations and modifications of a major character and outfitting related thereto, shall meet the requirements for a ship constructed on or after 1 July 1986 in so far as the Administration deems reasonable and practicable. 3 A ship irrespective of the date of construction, which is converted to a chemical tanker shall be treated as a chemical tanker constructed on the date on which such conversion commenced.

20 20 Regulation 10 Requirements for chemical tankers 1 A chemical tanker shall comply with the requirements of the International Bulk hemical ode and shall, in addition to the requirements of regulation I/8, I/9, and I/10, as applicable, be surveyed and certified as provided for in that ode. For the purpose of this regulation, the requirements of the ode shall be treated as mandatory. (See note below) 2 A chemical tanker holding a certificate issued pursuant to the provisions of paragraph 1 shall be subject to the control established in regulation I/19. For this purpose such certificate shall be treated as a certificate issued under regulation I/12 or I/13. Note: Offshore Support Vessels Offshore support vessels used for transport and handling of limited amounts of hazardous and noxious liquid substances in bulk can fulfil IMO Res. A. 673 (16) instead of SOLAS VII part B. The resolution has the title: Guidelines for the transport and handling of limited amounts of hazardous and noxious liquid substances in bulk on offshore support vessels. Definitions and limitations as well as a list of substances allowed to be carried are found in the annex to the resolution.

21 21 Danish national requirements: From Meddelelser B fra Søfartsstyrelsen: Afsnit B Konstruktion og udrustning af skibe, der transporterer farlige flydende kemikalier i bulk Regel 8 Definitioner Ved anvendelse af dette afsnit gælder, medmindre andet udtrykkeligt er bestemt, følgende definitioner: 1 "Den Internationale Bulk hemical ode (IB koden)" betyder "The International ode for the onstruction and Equipment of Ships arrying Dangerous hemicals in Bulk" vedtaget af Organisationens maritime sikkerhedskomité ved Res. MS.4(48), som kan ændres af Organisationen, forudsat at sådanne ændringer er vedtaget, trådt i kraft og bragt til virkning i overensstemmelse med bestemmelserne i artikel VIII i SOLAS konventionen vedrørende de ændringsprocedurer, der finder anvendelse på andre tillæg end kapitel I. 2 "Kemikalietankskib" betyder et lastskib indrettet til eller egnet for og anvendt til transport af ethvert flydende produkt, der er opregnet i kapitel 17 i den internationale Bulk hemical ode. 3 I regel 9 betyder "skib, der er bygget" skibe, hvor kølen er lagt, eller et tilsvarende byggestadium er opnået. 4 "På et tilsvarende byggestadium" betyder det stadium, hvor.1 et byggeri, der kan identificeres med et bestemt skib, påbegyndes, og.2 samling af dette skib er påbegyndt, omfattende mindst 50 tons eller 1% af den anslåede samlede skrogvægt, hvis denne er mindre. Regel 9 Anvendelse på kemikalietankskibe 1 Medmindre andet udtrykkeligt er bestemt, finder dette afsnit anvendelse på kemikalietankskibe bygget den 1. juli l986 eller senere og omfatter tillige skibe med en bruttotonnage under 500. Sådanne tankskibe skal opfylde bestemmelserne i dette afsnit samt enhver anden relevant bestemmelse i nærværende regelværk. 2 Ethvert kemikalietankskib, der er under reparation, ombygning, forandring og udrustning i forbindelse hermed, skal uanset byggetidspunkt fortsat opfylde de bestemmelser, der tidligere gjaldt for skibet. Disse skibe skal, hvis de er bygget før 1. juli l986, som hovedregel opfylde forskrifterne for skibe bygget på eller efter dette tidspunkt i samme udstrækning som inden, de undergik sådanne reparationer, ombygning, forandringer eller udrustning. Reparationer, ombygning og forandringer af væsentligt omfang, samt udrustning i forbindelse hermed, skal opfylde forskrifterne for skibe bygget den 1. juli l986 eller senere, for så vidt Administrationen anser dette for rimeligt og praktisk muligt. 3 Et skib, som ændres til et kemikalietankskib, skal uanset byggetidspunkt betragtes som et kemikalietankskib bygget på det tidspunkt, hvor en sådan ændring påbegyndes. 4 Eksisterende kemikalietankskibe, bygget før 1. juli 1986, skal opfylde bestemmelserne i "ode for the construction and Equipment of Ships arrying Dangerous hemicals in Bulk (B ode) " med senere ændringer Regel 10 Krav til kemikalietankskibe 1 Kemikalietankskibe skal opfylde forskrifterne i Den Internationale Bulk hemical ode (IB koden) og skal, foruden at opfylde de relevante bestemmelser i kapitel I, regel 8, 9 og 10, synes og certificeres, som foreskrevet i denne kode. 2 Kemikalietankskibe, der er forsynet med et certifikat udstedt i overensstemmelse med bestemmelserne i stk. 1, skal være omfattet af den kontrol, der er foreskrevet i henhold til kapitel I, regel 9. Med henblik herpå skal et sådant certifikat betragtes som et certifikat udstedt i henhold til kapitel I, regel 12 eller 13.

22 22 argo- and stripping pipes

23 23 IB-code The IB-code (International ode for the onstruction and Equipment of Ships arrying Dangerous hemicals in Bulk) has several purposes. First and most it is a construction code, which ensures that all chemical tankers are built to high international standards. (For chemical tankers build before 1 of July 1986 the B-code applies) Furthermore the code has a lot of information which influences the daily operation. The IB code was thoroughly amended with effect from 1 January 2007 due to revision of MARPOL Annex II. The code consists of 21 chapters plus an appendix with the model form of the International ertificate of Fitness for the carriage of dangerous chemicals in bulk (.o.f.) and also different Standards and Guidelines relevant to the code. ere is for example shown an example of an optional shipping document for the purpose of MARPOL Annex II and the IB ode. During the normal operation the typical use of the code will be a check to see if the chemical the vessel is about to load will demand any special precautions.

24 24 The Procedure is: 1. Find the chemical in the index, chapter 19: Extract from hapter 19:

25 25 In the index you will find a reference to hapter 17 or 18 of the IB-code or you will find another name for the chemical. The fourth column gives the UN Numbers of products which were available up to February If the name of the chemical is not in the index the shipper must be contacted to see if he has another name for the chemical. If the chemical cannot be found in the code the vessel is not allowed to transport it, unless a tripartite agreement is made by the flag state s administration and the administrations of the port states involved in the transport (IB and MARPOL Annex II regulation 6.3). The latest edition of the MEP.2/irc. contains some lists with associated pollution categories and minimum carriage requirements which have been established through Tripartite Agreements and registered with the IMO Secretariate. The MEP.2/irc. is in fact just as important to have on board as the IB ode! If the chemical is listed in chapter 17 or if the chemical is listed in chapter 18 with a pollution category Z, the product must be listed on the ship s ertificate of Fitness. If the product is listed in chapter 18 without any pollution category ( other Substance OS) there are no restrictions for transport other than commercial restrictions. List of products to which the code does not apply, (hapter 18) The products mentioned in chapter 18 are products which in spite of their chemical nature and names are not considered dangerous. This means that those products in principle may be transported in any tanker except for the fact that some of them present a minor pollution hazard. If the product has a Pollution ategory Z it must be listed on the vessel s ertificate of Fitness. If the ship is not a chemical tanker (i.e. holds no of) the product must be listed on a NLS-certificate ( Noxious Liquid Substances). Of course the equipment of the vessel such as coating, packings, pumps etc. is decisive as to which products actually can be carried. From 2007 chapter 18 only contains a little less than 40 substances compared to more than 250 substances before that date.

26 26 Extract from the IB-code, chapter 18

27 27 2. If the product is listed in chapter 17 the next step is to check the requirements in this chapter. Summary of minimum requirements (hapter 17) olumn a: Product Name: The Proper Shipping name (PSN). See comments above. (olumn b: ) (olumn b is deleted with effect from 1 January olumn b showed the UN number, if applied. See comments given to the Index above.) olumn c: Pollution ategory: The pollution category can be X, Y or Z according to the criteria laid down in MARPOL s Annex II. The pollution categories are only kept updated in this list and not in MARPOL. olumn d: Indicates whether the product is included in hapter 17 azards: due to Safety problems ( S ) or due to Pollution problems ( P ), - or even both ( S/P ). olumn e: Ship Type: Type 1 ships hemical tankers will be assigned one or more ship types according to the ship s construction. are constructed and equipped to carry the most dangerous or reactive chemicals which require the most extensive precautions to avoid spill if the vessel is involved in a collision or grounding. Furthermore the requirements to damage survival capabality and buoyancy after a collision or grounding are rather stringent

28 28 On the figure is shown the most important demands to the construction of the hull and the cargo tank s location. IMO Ship Types Type 2 ships Type 3 ships are constructed and equipped to carry less dangerous product than type 1, but nevertheless so dangerous that the vessel must be capable of surviving minor collisions and grounding without leaking cargo to the environment. Depending on the size of the vessel type 2 ships are subject to almost the same requirements for damage stability as type 1 ships. are constructed to carry products that represent a greater danger than oil products and consequently requires some protection. A type 3 vessel has no demands to the location of the cargo tanks, but is subject to some requirements as to damage stability.

29 29 olumn f: Tank Type: Independent tanks Integral Tanks In addition to the requirements to the hull construction and the location of the cargo tanks, also the tank construction is classified. Independent tanks Integral tanks (tank type 1G) means tanks which are not part of the hull structure. An independent tank is not essential to the structural completeness of the hull. (tank type 2G) are tanks which form part of the ships hull and which may be stressed in the same manner and by the same loads which stress the hull. Gravity tank means a tank having a design pressure not greater than 0.7 bar gauge at the top of the tank. It may be an integral tank or an independent tank. Pressure tank olumn g: Tank vents: means a tank having a design pressure greater than 0.7 bar gauge. A pressure tank should be an independent tank. (A pressure tank is not specified for any of the products currently in the IB-code.) The requirements for tank vents (Open or ontrolled) is explained in IB ode hapter 8.

30 30 olumn h: Tank environmental ontrol: Inert: Pad: Dry: Vent: olumn i: Electrical equipment: The column offers one of four possibilities. The tank and associated piping must be inerted by filling them with an appropriate gas or vapour, which will not support combustion or react with the cargo. The tank and piping must be filled with an appropriate gas or liquid, which separates the cargo from the air and this condition must be maintained during the voyage. The tanks and piping must be maintained at a dewpoint of 40 or below. The ullage space of the tanks must be ventilated either by natural or forced ventilation. This column states the temperature class and electrical apparatus group for equipment to be used in gas dangerous areas. Furthermore it is stated whether the flashpoint is above 60 or not. hapter 10 of the IB-code deals in detail with the requirements for electrical equipment. olumn j: Gauging: Open: Restricted: losed: Indirect: Also this column offers one of four possible devices. A method of gauging which will expose the gauger to the cargo or its vapour. An example is the use of a normal ullage hatch. A device which penetrates the tank, but only exposes the user to small amounts of vapour. Examples are portable gauging devices mounted on sounding pipes with a valve. Devices that penetrate the tank but which do not allow any vapour to be released during their use. Examples are floattype systems, pressure sensors and tank radars. A device which does not penetrate the tank and is independent of the tank as for example a flow-meter. Indirect devices are not presently specified for any of the products in the IB-code, but may be used in stead of closed devices. olumn k: Vapour detection: This column specifies whether the vessel must have on board special detector equipment for the product. If the column specifies F, the vessel must have at least two instruments capable of checking for a flammable atmosphere of the product. If the column specifies T, the vessel must have at least two instruments which are usable for testing for toxic concentrations. If it is impossible to obtain measuring equipment for a specific gas where this column specifies T, the ship s ertificate of Fitness will reflect this by requiring additional supply of breathing-air. In either case one of the instruments can be a fixed installation.

31 31 column l: Fire protection: Specifies which kind of fire-fighting media will be the best for the product. All chemical tankers must have a foam-system, but addition of some products to the ertificate of Fitness could mean requirements for large amounts of dry powder or for a water-spray system. (olumn m:) (Deleted from 1 January 2007) Materials of construction: olumn n: Respiratory and eye protection: olumn o: Special requirements: Whenever Yes appears in this column it means that the ship must have suitable respiratory and eye protection for every person on board. The equipment must include selfcontained breathing apparatuses with at least 15 minutes air supply. This column refers to special requirements from the code s chapter 15 and/or 16. The special requirements vary considerably from product to product, and as quite a lot of them have operational significance it is absolutely necessary to check these requirements for each product. Amended IB hapters 17, 18 and 19 As many new substances have been introduced since the current edition of the IB code was issued in 2007, they need to be listed in the MEP.2/irc. and stay there, until an amended IB code will be released. Therefore, with effect from 1 July 2014 the existing text of IB hapters 17, 18 and 19 will be replaced by new chapters 17, 18 and 19. ertificate of Fitness When a vessel has been surveyed and found to match the requirements of the IB-code a "ertificate of Fitness" is issued either by the National Authority or by the lassification Society on behalf of the National Authority. Attached to the ertificate of Fitness is a List of argoes. This list states the tanks that may be used for the carriage of a product from chapter 17 of the code (And category Z product from chapter 18). The certificate will also mention any additional requirements or exemptions valid for the ship. The ertificate of Fitness is subject to the same surveys as most of the other statutory certificates, i.e. Annual, Intermediate and Periodical surveys. The of is issued for a 5-year period and the IB-code states categorically, that no extension of the 5-year period should be permitted, meaning that it is of utmost importance to make sure that the surveys are carried out in due time.

32 32 Below is shown an example of the first pages of a ertificate of Fitness and also a page from the accompanying product list.

33 33 Please note: with effect from 1 July 2014 hapters 17, 18 and 19 of the IB code are updated to reflect the amendments to the entries since 2007 when the IB code was amended as a consequences of the revision of MARPOL Annex II. The vessels existing ertificate of Fitness shall be replaced by revised certificates as a qonsequence of the entry into force of the amendments to chapters 17 and 18 of the IB code.

34 34 The notes in the product list reflect various operational notes from the IB-code and the lassification Society s interpretation of these notes.

35 35 hemistry Most people have learnt about chemistry at one time in their career, but many have later on almost forgot more than they have learnt. That is a pity because just a tiny knowledge of the most elementary chemistry can explain a lot of why and how when dealing with the operation of chemical tankers. Of course chemistry is decisive for how a cargo can react with itself, with other cargoes, air, water, cleaning additives, and chemistry can help to explain the results of wall wash tests. To make it short, - cargoes can be divided into organic and inorganic substances where organic substances are molecules containing one or more carbon atoms ( atoms) (except for O and O 2 ) and inorganic substances do not have any carbon atoms in their chemical composition. The majority of cargoes carried on chemical tankers are organic substances where a main group is hydrocarbon. ydrocarbons ydrocarbons are compounds containing only the elements carbon and hydrogen. A very large number of compounds are known. Aliphatic hydrocarbons - Aromatic hydrocarbons - Saturated hydrocarbons - ydrocarbons are insoluble in water (benzene is slightly soluble in water). They are not toxic, except benzene. There are several subdivisions of hydrocarbons like: chain-like skeleton of -atoms like for instance pentane benzene and its derivatives, e.g. toluene having no spare combining capacity therefore chemically unreactive: names all end in ane. E.g. hexane. Unsaturated hydrocarbons - having one or more double bonds, therefore more reactive. Names end in ene. E.g. hexene (or diene when two double bonds like butadiene) Alicyclic hydrocarbons - having a ring structure in the molecule like cyclohexane, but excluding benzene and its derivatives Alkanes or Paraffins The simplest hydrocarbons are called alkanes or paraffins. Nomenclature: ending in -ane. The molecules are chain shaped, completely saturated with : Methane ( 4 ) Ethane ( 2 6 )

36 36 Propane ( 3 8 ) Butane ( 4 10 ) The general formula for the alkanes is n 2n+2 The 1 to 4 substances i. e. methane, ethane, propane and butane are gases at ambient temperatures. The next ones are liquids and have their names from the number of atoms in the molecules taken from ancient Greek. E. g. pentane (5), hexane (6), heptane (7), octane (8), nonane (9), decane (10), undecane (11) etc. From 15 the straight chained molecule substances are more or less solid (waxes). If a hydrogen atom is removed from an alkane molecule you have a radical, an unsaturated hydrocarbon. The names are derived from the alkane names but with the ending -yl. They cannot exist as pure substances, but are connected to other radicals or atoms. The most common are: Methyl ( 3 -) Ethyl ( 2 5 -) Propyl ( 3 7 -) Butyl ( 4 9 -) Substances with the same gross formula are called isomeric. They are common in the alkane family from 4 and up where branched chained molecules are common. A simple branched chained alkane is called an iso-alkane. Two different iso-pentanes exists: Both have the gross formula 5 12 but quite different geometrical shape. The common name is iso-pentane. The first one is also more correctly called 2-methylbutane, as it

37 37 might be considered as a butane molecule with a methyl group attached to the second carbon atom. The latter might in the same way be considered as a propane molecule with two methyls attached, wherefore it is called 2,2-dimethylpropane. The commercial name is neopentane. Iso-products often have a lower boiling- and freezing point and a different density than the normal alkane. ycloalkanes (Naphtenes) Besides the chain shaped hydrocarbons also circular shaped molecules exist. They have the same names as the normal alkanes but with the prefix "cyclo-". The most simple are the gases cyclopropane and cyclobutane, but cyclopentane and cyclohexane occur much more frequent. yclopropane ( 3 6 ) yclobutane ( 4 8 ) yclopentane ( 5 10 ) yclohexane ( 6 12 ) is-1,2-dimethylcyclohexane 6 10 ( 3 ) 2 yclo compounds are used as solvents, but also as base products in the chemical and medical industry by exchanging hydrogen atoms with other atoms or molecules.

38 38 The latter chemical name explains the molecular configuration as a hexane ring with two (di) methyl groups attached to two adjacent (1,2) carbon atoms and pointing to the same side (cis). Alkenes or olefins In a hydrocarbon molecule the carbon atoms might also use two of their bonds for connection to the neighbouring carbon atom. Such a double bond is weaker than the normal single bond, and the molecules become unstable. ydrocarbons with one double bond are called alkenes, former alkylenes. When writing an alkene formula the double bond is shown by two dots, one above the other. Below examples on different alkenes: Ethene (ethylene) 2 : 2 Propene (propylene) 2 : 3 ompounds containing double bonds are also called unsaturated hydrocarbons or monomers. If the double bonds break, typically at elevated temperatures or if inhibitor is not present in sufficient amount, the product might polymerize i.e the monomer turns into a polymer that is very long chains of molecules, and the product turns from the gaseous or liquid state into a solid. From butene three different isomers might be derived viz.: 1-Butene (n-butylene) 2 : 2 3 is-2-butene 3 : 3 Trans-2-butene 3 : 3 From pentene and hexene more different isomers might be derived, some of them are shown on next page.

39 39 is-2-pentene 3 : 2 3 Trans-2-pentene 3 : 2 3 Trans-3-hexene 3 2 : 2 3 Alkenes are very much used in the synthetic industry for plastic and fibre production. Aromatics Among the ring shaped molecules the aromatics make a special group. They are generally more toxic than the equivalent alkanes. The base element in this family is the so called benzene ring made up by 6 carbon atoms bonded in a special way so that each carbon atom only have one free bond for hydrogen or radicals. Benzene and toluene are the most well-known and both are shipped in large amounts. Benzene ( 6 6 ) Toluene ( 7 8 ) or MethylBenzene ( ) Also the xylenes are very much used as solvents. They consist of a benzene ring and two methyl groups. Three different isomers exist viz.:

40 40 Orthoxylene ( 8 10 ) or 1,2-dimethylbenzene (1,2-6 4 ( 3 ) 2 ) mp: -25 bp: 144 Methaxylene ( 8 10 ) or 1,3-dimethylbenzene (1,3-6 4 ( 3 ) 2 ) mp: -47,4 bp: 138,8 As seen from the above-mentioned xylene, isomers may have rather different properties. Therefore, when isomers are possible, information about gross name or gross formula is not enough, but a full description on the chemical composition of the cargo must be given. More benzene rings might be connected to each other. Most simple and well known is the naphthalene, made up by two benzene rings. Paraxylene ( 8 10 ) or 1,4-dimethylbenzene (1,4-6 4 ( 3 ) 2 ) mp: 13,2 bp: 138,5 Naphtalene ( 10 8 ) Unsaturated aromatics When alkenes (or olefins) chains are attached to benzene molecules the substance is called unsaturated aromatic. Examples are Styrene, Vinyltoluene, methyl styrene. Unsaturated aromatics are liable to polymerisation.

41 41 Inorganic ompounds The only ones likely to form tanker cargoes are: Solution of alkalis like caustic soda, sodium hydroxide Strong acids like hydrochloric acid, nitric acid and sulphuric acid Fairly strong acids like phosphoric acid Acids and Alkalis Acids are defined as compounds that yield hydrogen ions ( + ) when dissolved in water. In the same way alkalis are defined as compounds, which are able to combine with hydrogen ions. Generally acids and alkalis are corrosives i.e. substances that may be damaging to metals, organic materials or living tissues. Example on reaction with water: Acid (ydrochloric acid): l + + l - Alkali (sodium hydroxide): NaO Na + + O - (austic soda) The following diagram shows how acids might be formed by oxidation of non-metals and alkalis by oxidation of metals: ELEMENTS METALS NON - METALS REATION WIT O 2 METAL OXIDE NON - METAL OXIDE REATION WIT 2 O METAL YDROXIDE AID NEUTRALIZATION SALT + WATER

42 42 Mg (Magnesium) S (Sulphur) REATION WIT O 2 MgO (Magnesium oxide) SO 3 (Sulphur trioxide) REATION WIT 2 O Mg(O 2 ) (Magnesium hydroxide) 2 SO 4 (sulphuric acid) NEUTRALIZATION MgSO O Magnesium Sulfate + water E.g. ydrochloric acid + zinc: If acids and alkalis are mixed, they will more or less neutralize each other and make a salt plus water. E.g. ydrochloric acid and caustic soda: l + NaO Na + + l O If the amounts are adjusted to a neutral solution, salt water is formed. Many metals or substances containing metal (e.g. certain coatings) are dissolved or react chemically with acids and alkalis. 2l + Zn l - + Zn 2 + Znl 2 By this reaction free hydrogen is formed so that apart from the damaging corrosive effect also danger of explosion might be expected, even though most acids and alkalis are not flammable. The strength of acids and alkalis is measured in p, which is defined as the logarithm of the hydrogen ion concentration with opposite sign. The p value might also be expressed as the number of litres that contain 1 g + denominated exponential. E.g. if l contain 1 g + the p = 4 as = Practically only p values between 0 and 14 are used, and p = 7 designate a neutral solution, a p value smaller than 7 an acid solution and a p greater than 7 designate an alkaline solution.

43 43 p values of some well known substances: Substance p Beer 4-5 ows milk Detergents Drinking water Egg white Gastric juice 1-3 ydrochloric acid 0.1 Lime juice Potato Sea water Sodium ydroxide 14 Sulphuric acid 0.3 Vinegar In the chemical transport business other methods are often used to tell the strength of acids, or to tell the acid content of the product, - e.g. the AV or FFA. AV = Acid Value is a number stating the amount in grams of KO (potassium hydroxide) necessary for neutralizing 1 kg of the product. FFA = Free Fatty Acid is an indication of the percentage of free fatty acids in organic oils and fats. The AV number is generally twice the FFA number taken from the same sample. Some properties of common acids and alkalis ydrochloric acid l: The pure product is a gas. Normally shipped in a 38 % concentration in water, which is a highly corrosive liquid. Sulphuric acid 2 SO 4 : Nitric acid NO 3 : Phosphoric acid 3 PO 4 : Acetic acid 3 OO: Dissolves most metals and forms hydrogen. Steel is resistant when concentration is higher than 80% Strong oxidizing agent. Dissolves most metals and forms hydrogen. Stainless steel is resistant. Dissolves metals and forms hydrogen especially at elevated temperatures. Stainless steel is normally resistant but impurities (especially chlorides) in commercial products might cause corrosivity. Dissolves most metals, but not aluminium. Vapours are explosive (LEL 4 %). Stainless steel is resistant. Sodium hydroxide (caustic Solid crystalline substance, normally transported as a 50

44 44 soda) NaO: Potassium hydroxide (caustic potash) KO: Ammonia (ammonia aqueous) N 4 O: % solution corrosive to most organic substances and many metals especially aluminium. Stainless steel or epoxy coating is resistant. Nearly same properties as NaO. Ammonia (N 3 ) dissolved in water. orrosive to copperzinc- and aluminium compounds. Ammonia vapours are combustible, LEL = 16%, UEL = 25 % but the energy required for ignition is very high, so it is unlikely that ammonia vapours will ignite. Inserted on the next page is a copy of the Periodic Table of the Elements:

45 45

46 46 hemical Families Alcohols (20) All the hydrocarbons mentioned above consisted of carbon and hydrogen only. Very often also other elements are present in the organic compounds e.g. Oxygen, nitrogen, halogens etc. These compounds may be grouped in different chemical families. In the following, chemical families often carried will be discussed. The grouping is also in accordance with the US oast Guard ompatibility hart and the numbers in ( ) refer to that. An alcohol is derived from a hydrocarbon by substituting a - atom by the hydroxyl group -O. Their names have the suffix -ol. They are generally toxic but in a very varying degree. They are all flammable. The following are some of the more common alcohols: O Methanol (methylalkohol) 3 O O Ethanol (ethylalkohol) 2 5 O 2-propanol (iso-propylalkohol) ( 3 ) 2 O O Also some of the higher alcohols, such as 2-ethylhexanol (octanol) are commonly encountered. Glycols (20) have 2 O groups and are also called dihydric alcohols. Some glycols are very toxic. A typical examples from this group is: O O Ethyleneglycol 2 O 2 O Glycerol (20) Phenols and cresols (21) is a trihydric (three O groups) alcohol. It is non toxic. Used widely in the explosives manufacturing business. Formally these substances also belong to the alcohol family, but generally they are considered as an independent group. The phenols consists of a benzene ring with one or more -O group(s) attached. resols furthermore have a methyl group attached to the benzene ring.

47 47 The phenols are acidic as they are able to yield +, they are very toxic also by skin contact. The most well-known is phenol (carbolic acid) 6 5 O and naphtol 10 7 O, which has two benzene rings linked. resol, also called methyl phenol, has the formula O and is found in three isometric compounds. Ethers (41) are alcohol anhydrides as they may be derived from alcohols by elimination of water thereby having the generic formula ROR where R and R are organic radicals: O The most important is ethylether 2 5 -O- 2 5 the same as ether in common speaking. An other common ether is 1,4-dioxane 4 8 O 2, a glycol anhydride with a ring shaped molecule. The formula is often more correctly written in the following way: O 2 2 O 2 2 All ethers are toxic, more or less, typical with a narcotic effect, and the vapours form flammable mixtures with air. Ketones (18) is a class of liquid compounds in which the carbonyl group Ois attached to two carbon atoms i. e. the denominating group is inside the hydrocarbon chain. The substances have very different properties, but most of them are narcotic and flammable. The simplest and most well-known ketone is acetone: O Dimethylketone (acetone) 3 O 3 Another commonly transported ketone is the methyl ethyl ketone 3 O 2 5, which often is abbreviated MEK. Organic acids (4) The most important group of organic acids contains in the molecule the carboxyl group -OO or more correctly O which always will be at the end of the chain. The strongest organic acid is formic acid -OO. The strength of the acids decreases with increasing number of carbon atoms. O

48 48 The most well known are acetic acid 3 -OO and propionic acid 2 5 -OO. Also two -OO groups are possible e. g. the oxalic acid OO- OO or malonic acid OO- 2 -OO. Anhydrides (11) If water is removed from acid, an acid anhydride is formed. They may be very toxic and might react violently with water giving off heat. The most common are acetic anhydride ( 3 O) 2 O and propionic anhydride ( 3 2 O) 2 O. The constitutional formula of acetic anhydride is as follows: O O O Esters (34) Organic compounds corresponding in structure to a salt in the inorganic chemistry. Esters are considered as derived from acids by the exchange of the replaceable hydrogen for an organic radical. Their names normally are derived from acid names with the suffix -ate Esters have very different properties, some are very volatile with a narcotic effect if inhaled. They often have a pleasant odour, and are generally not very reactive. Waxes are esters derived from fatty acids and alcohols, while fats are esters from fatty acids and glycerol. ommonly carried are: O O Methylacetate 3 OO- 3 O O Ethylformate OO- 2 5 and also some of the phthalates such as Diisooctylphthlatlate (DIOP). Alkylene oxides (16) (Epoxides) Organic compounds containing a reactive group resulting from the union of an oxygen atom with two other atoms (usually carbon) that are joined in a triangle. haracteristic properties are a very wide flammability range, burns violently and are very difficult to extinguish by smothering due to the oxygen content. Transportation is carried out in inerted tanks. eating should be avoided. The only product normally encountered in chemical tankers is:

49 49 Propyleneoxide 3 6 O O Aldehydes (19) is a broad class of organic compounds having the generic formula RO, and characterized by the unsaturated carbonyl group O They are all very toxic with vapours irritating to the eyes and mucous membranes. Most of them are soluble in water and alcohol and some of them are able to polymerize. The smell is characteristically pungent. The simplest as formaldehyde O and acetaldehyde 3 O are transported as water solutions, while propanal 2 O, butanal O and furfural 4 3 OO are transported as pure products. Amines (7, 8, & 9) Aliphatic amines (7) Aromatic amines (9) A class of organic compounds of nitrogen that may be considered as derived from ammonia (N 3 ) by replacing one or more of the hydrogen atoms with alkyl groups. As a general rule, hydrocarbons containing nitrogen are more toxic than equivalent compounds without nitrogen. Amines are subdivided into subgroups according to the organic radicals connected to the nitrogen atom. consists of one or more alkyles joined to the nitrogen atom e. g. ethyl amine 3 2 N 2 and diethylamine ( 2 5 ) 2 N. have one or more benzene groups. Example: aniline 6 5 N 2 and pyridine N() 4 Alkanol amines (8) a compound such as ethanolamine O 2 2 N 2 or triethanolamine (O 2 2 ) 3 N, in which nitrogen is attached directly to the carbon of an alkyl alcohol. Amides (10) are organic compounds containing the group -ON 2 e. g.: O N Acetamide 3 -ON 2

50 50 yanates (12) Acrylates (14) Allyls (15) Epichlorohydrin (17) Vinyl halides (35) alogenated hydrocarbons (36) Glycol ethers (40) Example: are compounds containing nitrogen in the form of -ON. Most of them are iso compounds i. e. iso cyanates. Frequently carried is toluene-2,4-diisocyanate (NO) 2. are monomer esters from acrylic acid. The denominating molecular structure is 2 :OO-. Generally transported is methylacrylate 2 :OO 3. Acrylates must normally be inhibited during transport. are derived from propene (=allene). Polymerizable substances with the group 2 : 2 -. Known examples are: Allylalcohol 2 : 2 O and acrylonitrile 2 :-N. 2 O 2 l is an epoxy compound that is able to polymerize at elevated temperatures. It is poisonous and flammable and reacts with several other cargoes. are derived from vinyl 2 :- (= ethene) with halogens attached to the free bonds. Most of them are gases at ambient temperatures. ommon are: Vinyl chloride 2 :l and vinylidene fluoride 2 :F 2. ompounds between hydrocarbons and halogens. Some of them are poisonous especially as they decompose when heated and forms toxic gases. Some of them are used in fire fighting (they quench the flames) others are used as refrigerants. Regularly transported is ethylene dichloride (ED) l 2 2 l are transported widely under the trade name "cellosolve" and are mostly used in the paint industry. When transported they are often mixed. They are chemical stable compounds but also very often both flammable and harmful to the health. Ethylene glycol dimethyl ether 3 O 2 2 O 3. Nitrocompounds. (42) are compounds with nitrogen apart from those already mentioned. The radical -NO 2 is seen frequently. As mentioned earlier all nitrogenhydrocarbons should be regarded as toxic especially in a fire situation in which different nitrogen oxides may be formed. Example: Nitrobenzene 6 5 NO 2.

51 51 Water solutions. (43) ompatibility hart This name covers a great variety of many different substances. The only common property is that they are all water-soluble and contain water. They should not be stowed adjacent to cargoes reacting with water. The properties of a solution might be quite different from those of the pure product. If chemicals are mixed in tanks or pipelines, the resulting chemical reaction might be very violent, high temperatures or pressure might arise or dangerous substances or vapours might be evolved. The IB code gives no help on this problem; it simply mentions that cargoes or slops, which dangerously react with each other, should be separated by an intervening compartment that does not contain a reactive substance. US oast Guard, Department of Transportation has regulated this problem in the ode of Federal Regulations, 46 FR 150. The cargoes are divided into chemical groups or families and group numbers 1-22 represent reactive chemicals, while are products that do not react mutually with each other. The missing numbers are reserved for future extensions of the chart. Using the ompatibility hart Examples: If you wish to investigate whether two cargoes are compatible or not, you must find the group numbers in table 1. If both group numbers are between 30 and 43 incl. the products are compatible, and it is then not necessary to use the chart. If both group numbers are not between 30 and 43 you enter with one group number in the left side and the other from the top of the chart. An "X" in the chart means that the two products are not compatible with each other, unless informed otherwise in the Appendix 1 - "Exceptions to the chart". If the intersection is blank, there will normally be no problems with compatibility, but there might be exceptions which also are mentioned in App. 1. A foot note "2" in table 1 means that the substance should be checked further in App. 1. Group ompatible butyraldehyde - acetic acid 19/4 yes allyl alcohol / toluene diisocyanate 15/12 no decene / ethyl benzene 30/32 yes ethanolamine / acetone 8/18 yes ammonia / dimethylformamide 6/10 no

52 52 Updated table1 If two or more non compatible cargoes have to be loaded, they should be separated from each other by two barriers such as a cofferdam, an empty tank, a piping tunnel or a tank containing a cargo compatible with both other cargoes. Isolation across a cruciform joint is equivalent to isolation by two barriers. Also the piping and venting system from the two incompatible cargoes has to be separated by e. g. Removing a valve or spool piece and blanking off the pipe ends or Installing two spectacle flanges in series with a means of detecting leakage into the pipe between the spectacle flanges. A "Seutelven" valve is usable. The US oast Guard regulations apply in US waters only, but are widely used in other parts of the world, also in Europe. on you will find an updated 46FR150 Seut Elven flange Spool piece and Seut Elven flanges

53 53

54 54 Table I to Part 150 Alphabetical List of argoes hemical name Group No. Foot note RIS ode Related RIS odes Acetaldehyde 19 AAD Acetic acid 4 2 AA Acetic anhydride 11 AA Acetochlor 10 AG Acetone 18 2 AT Acetone cyanohydrin 0 1, 2 AY Acetonitrile 37 ATN Acetophenone 18 AP Acrolein 19 2 ARL Acrylamide solution 10 AAM Acrylic acid 4 2 AR Acrylonitrile 15 2 AN Acrylonitrile-Styrene copolymer dispersion in Polyether polyol 20 ALE Adiponitrile 37 ADN Alachlor 33 AL Alcohols (13+) 20 ALY Including: Oleyl alcohol (octadecenol) Pentadecanol Tallow alcohol Tetradecanol Tridecanol Alcoholic beverages 20 Alcohol polyethoxylates 20 APU/APV/APW/AET Alcohol polyethoxylates, secondary 20 AEA/AEB Alkanes (6-9) 31 1 ALK Including: eptanes exanes Nonanes Octanes n-alkanes (10+) 31 1 ALJ Including: Decanes Dodecanes eptadecanes Tridecanes Undecanes iso- & cyclo-alkanes (10-11) 31 1 AKI iso- & cyclo-alkanes (12+) 31 1 AKJ Alkane (14-17) sulfonic acid, sodium salt solution 34 AKA Alkaryl polyether (9-20) 41 AKP Alkenyl(11+)amide 11 AKM Alkenyl(16-20)succinic anhydride 11 AA Alkyl acrylate-vinyl pyridine copolymer in Toluene 32 AAP Alkyl(8+)amine, Alkenyl (12+) acid ester mixture 34 AAA Alkylaryl phosphate mixtures (more than 40% Diphenyl tolyl 34 APD phosphate, less than 0.02% ortho-isomer) Alkyl(3-4)benzenes 32 AK Including: Butylbenzenes umene Propylbenzenes Alkyl(5-8)benzenes 32 AKD Including: Amylbenzenes eptylbenzenes exylbenzenes Octylbenzenes Alkyl(9+)benzenes 32 AKB Including: Decylbenzenes Dodecylbenzenes Nonylbenzenes Tetradecylbenzenes

55 55 hemical name Group No. Foot note RIS ode Related RIS odes Tetrapropylbenzenes Tridecylbenzenes Undecylbenzenes Alkylbenzene, Alkylindane, Alkylindene mixture (each 12-17) 32 AI Alkylbenzenesulfonic acid 0 1, 2 ABS/ABN Alkylbenzenesulfonic acid, sodium salt solutions 33 ABT Alkyl dithiothiadiazole (6-24) 33 ADT Alkyl ester copolymer (4-20) 34 AES Alkyl(7-9) nitrates 34 2 AKN ONE Alkyl(7-11) phenol poly(4-12)ethoxylate 40 APN Alkyl(8-40) phenol sulfide 34 AKS Alkyl(8-9) phenylamine in aromatic solvents 9 ALP Alkyl(9-15) phenyl propoxylate 40 Alkyl phthalates 34 Alkyl(10-20, saturated and unsaturated) phosphite 34 AKL Alkyl polyglucoside solutions 43 AGL/AGN/AGO/AGP/AGM Alkyl sulfonic acid ester of phenol 34 Allyl alcohol 15 2 ALA Allyl chloride 15 1 AL Aluminium chloride, ydrochloric acid solution 0 1 AS Aluminum sulfate solution 43 2 ASX ALM 2-(2-Aminoethoxy)ethanol 8 AEX Aminoethyldiethanolamine, Aminoethylethanolamine solution 8 Aminoethylethanolamine 8 AEE N-Aminoethylpiperazine 7 AEP 2-Amino-2-hydroxymethyl-1,3-propanediol solution 43 AL 2-Amino-2-methyl-1-propanol 8 APQ APR Ammonia, anhydrous 6 AMA Ammonia, aqueous (28% or less Ammonia) (IMO cargo 6 AM name),seeammonium hydroxide Ammonium bisulfite solution 43 2 ABX ASU Ammonium hydrogen phosphate solution 0 1 AMI Ammonium hydroxide (28% or less Ammonia) 6 AM Ammonium lignosulfonate solution,see alsolignin liquor 43 Ammonium nitrate solution 0 1 ANR AND/AMN Ammonium nitrate, Urea solution (containing Ammonia) 6 UAS Ammonium nitrate, Urea solution (not containing Ammonia) 43 ANU UAT Ammonium polyphosphate solution 43 AMO APP Ammonium sulfate solution 43 AME AMS Ammonium sulfide solution 5 ASS ASF Ammonium thiocyanate, Ammonium thiosulfate solution 0 1 AS Ammonium thiosulfate solution 43 ATV ATF Amyl acetate 34 AE IAT/AML/AAS/AYA Amyl alcohol 20 AAI IAA/AAN/ASE/APM Amylene, seepentene AMZ PTX tert-amyl methyl ether (see also,methyl tert-pentyl ether) 41 AYE Amyl methyl ketone, seemethyl amyl ketone AMK MAK Aniline 9 ANL Animal and Fish oils, n.o.s. 34 AFN Including: od liver oil Lanolin Neatsfoot oil Pilchard oil Sperm oil Animal and Fish acid oils and distillates, n.o.s. 34 AFA Including: Animal acid oil Fish acid oil Lard acid oil Mixed acid oil Mixed general acid oil Mixed hard acid oil Mixed soft acid oil Anthracene oil (oal tar fraction),seeoal tar 33 AO OR Apple juice 43 Aryl polyolefin (11-50) 30 AYF Asphalt 33 ASP AU

56 56 hemical name Group No. Foot note RIS ode Related RIS odes Asphalt blending stocks, roofers flux 33 ARF Asphalt blending stocks, straight run residue 33 ASR Asphalt emulsion (ORIMULSION) 33 ASQ Aviation alkylates 33 AVA GAV Barium long chain alkaryl(11-50) sulfonate 34 BA Barium long chain alkyl(8-14)phenate sulfide 34 B Behenyl alcohol 20 Benzene 32 BNZ Benzene hydrocarbon mixtures (having 10% Benzene or more) 32 BB BA Benzenesulfonyl chloride 0 1, 2 BS Benzene, Toluene, Xylene mixtures 32 2 BTX Benzene tricarboxylic acid, trioctyl ester 34 Benzylacetate 34 BZE Benzyl alcohol 21 BAL Benzyl chloride 36 BL Brake fluid base mixtures 20 BFX Bromochloromethane 36 BM Butadiene 30 BDI Butadiene, Butylene mixtures (cont. Acetylenes) 30 BBM Butane 31 1 BMX IBT/BUT 1,4-Butanediol, seebutylene glycol BDO BUG 2-Butanone, seemethyl ethyl ketone Butene, seebutylene IBL/BTN Butene oligomer 30 BOL Butyl acetate 34 BAX IBA/BN/BTA/BYA Butyl acrylate 14 1 BAR BAI/BT Butyl alcohol 20 2 BAY IAL/BAN/BAS/BAT Butylamine 7 BTY IAM/BAM/BTL/BUA Butylbenzene,seeAlky(3-4)benzenes 32 BBE AK Butyl benzyl phthalate 34 BP Butyl butyrate 34 BBA BUB/BIB Butylene 30 BTN IBL Butylene glycol 20 2 BUG BDO 1,3-Butylene glycol, seebutylene glycol BUG Butylene oxide 16 1 BTO Butyl ether 41 BTE Butyl formate 34 BFI/BFN Butyl heptyl ketone 18 BK Butyl methacrylate 14 1 BM BMI/BMN Butyl methacrylate, Decyl methacrylate, etyl-eicosyl methacrylate 14 1 DER mixture Butyl methyl ketone, seemethyl butyl ketone MBK Butyl phenol, Formaldehyde resin in Xylene 32 n-butyl propionate 34 BPN Butyl stearate 34 Butyl toluene 32 BUE Butyraldehyde 19 BAE BAD/BTR Butyric acid 4 BRA IBR gamma-butyrolactone 0 1, 2 BLA 9 Resinfeed (DSM) 32 2 NR alcium alkyl(9)phenol sulfide, polyolefin phosphorosulfide 34 PX mixture alcium alkyl salicylate, seealcium long chain alkyl salicylate AK (13+) alcium bromide solution, seedrilling brines DRB alcium bromide, Zinc bromide solution, seedrilling brine DZB (containing Zinc salts) alcium carbonate slurry 34 alcium chloride solution 43 S L alcium hydroxide slurry 5 O alcium hypochlorite solutions 5 Z/U/Y alcium lignosulfonate solution,see alsolignin liquor 43 alcium long chain alkaryl sulfonate (11-50) 34 AY alcium long chain alkyl phenates 34 AN/AW alcium long chain alkyl phenate sulfide (8-40) 34 PI alcium long chain alkyl salicylate (13+) 34 AK alcium long chain alkyl phenolic amine (8-40) 9 PQ alcium nitrate solution 34 NU

57 57 hemical name Group No. Foot note RIS ode Related RIS odes alcium nitrate, Magnesium nitrate, Potassium chloride solution 34 alcium sulfonate, alcium carbonate, ydrocarbon solvent 33 mixture amphor oil 18 PO anola oil, see rapeseed oil under oils, edible. aprolactam solution 22 LS aramel solutions 43 arbolic oil 21 BO arbon disulfide 38 BB arbon tetrachloride 36 2 BT ashew nut shell oil (untreated) 4 ON atoxid feedstock 36 2 XF austic potash solution 5 2 PS austic soda solution 5 2 SS etyl alcohol (hexadecanol), seealcohols (13+) ALY etyl-eicosyl methacrylate mixture 14 1 EM etyl-stearyl alcohol,seealcohols (13+) ALY hlorinated paraffins (10-13) 36 L hlorinated paraffins (14-17) (with 52% hlorine) 36 LJ hlorine 0 1 LX hloroacetic acid solution 4 M L/MA hlorobenzene 36 RB hlorodifluoromethane (monochlorodifluoromethane) 36 MF hloroform 36 RF hlorohydrins 17 1 D 4-hloro-2-methylphenoxyacetic acid, Dimethylamine salt solution 9 DM hloronitrobenzene 42 NO 1-(4-hlorophenyl)-4,4-dimethyl pentan-3-one 18 2 DP hloropropionic acid 4 PM LA/LP hlorosulfonic acid 0 1 SA hlorotoluene 36 I TM/TO/RN holine chloride solutions 20 O itric acid 4 IS IT lay slurry,see alsokaolin clay slurry 43 oal tar 33 OR OT oal tar distillate 33 DL oal tar, high temperature 33 oal tar pitch 33 TP obalt naphthenate in solvent naphtha 34 NS oconut oil, fatty acid 34 FA opper salt of long chain (17+) alkanoic acid 34 US FT orn syrup 43 SY ottonseed oil, fatty acid 34 FY reosote 21 2 T W/WD resols 21 RS RL/SL/SO resylate spent caustic 5 S resylic acid 21 RY resylic acid, dephenolized 21 AD resylic acid, sodium salt solution (IMO cargo name),seeresylate 5 S spent caustic resylic acid tar 21 RX rotonaldehyde 19 2 TA umene (isopropyl benzene), seepropylbenzene UM PBY 1,5,9-yclododecatriene 30 YT ycloheptane 31 1 YE yclohexane 31 1 X yclohexanol 20 N yclohexanone 18 yclohexanone, yclohexanol mixtures 18 2 YX yclohexyl acetate 34 Y yclohexylamine 7 A 1,3-yclopentadiene dimer 30 PD DPT yclopentadiene, Styrene, Benzene mixture 30 SB yclopentane 31 1 YP yclopentene 30 PE ymene 32 MP Decahydronaphthalene 33 DN Decaldehyde 19 IDA/DAL

58 58 hemical name Group No. Foot note RIS ode Related RIS odes Decane, seen-alkanes (10+) D ALJ Decanoic acid 4 DO Decene 30 DE Decyl acetate 34 DYA Decyl acrylate 14 1 DAT IAI/DAR Decyl alcohol 20 2 DAX ISA/DAN Decylbenzene,seeAlkyl(9+) benzenes 32 DBZ AKB Decyloxytetrahydro-thiophene dioxide 0 1, 2 DT Degummed 9 (DOW) 33 DG Dextrose solution,seeglucose solution 43 DTS GLU Diacetone alcohol 20 2 DAA Dialkyl(10-14) benzenes,seealkyl(9+) benzenes 32 DAB AKB Dialkyl(8-9) diphenylamines 9 DAQ Dialkyl(7-13) phthalates 34 DA Including: Diisodecyl phthalate Diisononyl phthalate Dinonyl phthalate Ditridecyl phthalate Diundecyl phthalate Dibromomethane 36 DB Dibutylamine 7 DBA Dibutyl carbinol, seenonyl alcohol NNS Dibutyl hydrogen phosphonate 34 DD Dibutylphenols 21 DBT/DBV, DBW Dibutyl phthalate 34 DPA Dichlorobenzene 36 DBX DBM/DBO/DBP 3,4-Dichloro-1-butene 36 DD DB Dichlorodifluoromethane 36 DF 1,1-Dichloroethane 36 D 2,2 -Dichloroethyl ether 41 DEE 1,6-Dichlorohexane 36 DX 2,2 -Dichloroisopropyl ether 36 DI Dichloromethane 36 DM 2,4-Dichlorophenol 21 DP 2,4-Dichlorophenoxyacetic acid, Diethanolamine salt solution 43 DDE 2,4-Dichlorophenoxyacetic acid, Dimethylamine salt solution 0 1, 2 DAD DDA/DSX 2,4-Dichlorophenoxyacetic acid, Triisopropano-lamine salt solution 43 2 DTI Dichloropropane 36 DPX DPB/DPP/DP/DPL 1,3-Dichloropropene 15 1 DPS DPU/DPF Dichloropropene, Dichloropropane mixtures 15 1 DMX 2,2-Dichloropropionic acid 4 DN Dicyclopentadiene,see also1,3-yclopentadiene dimer 30 DPT PD Diethanolamine 8 DEA Diethanolamine salt of 2,4-Dichlorophenoxyacetic acid solution, see2,4-dichlorophenoxyacetic acid, Diethanolamine salt solution Diethylamine 7 DEN Diethylaminoethanol (IMO cargo name),seediethylethanolamine 8 DAE 2,6-Diethylaniline 9 DMN Diethylbenzene 32 DEB Diethylene glycol 40 2 DEG Diethylene glycol butyl ether, seepoly(2-8)alkylene glycol DME monoalkyl(1-6) ether Diethylene glycol butyl ether acetate, seepoly(2-8)alkylene glycol DEM monoalkyl(1-6) ether acetate Diethylene glycol dibenzoate 34 DGZ Diethylene glycol dibutyl ether 40 DIG Diethylene glycol diethyl ether 40 Diethylene glycol ethyl ether, seepoly(2-8)alkylene glycol monoalkyl (1-6) ether Diethylene glycol ethyl ether acetate, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether acetates Diethylene glycol n-hexyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether Diethylene glycol methyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether Diethylene glycol methyl ether acetate, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether acetate DGE DGA DE DGM DGR DDE PAG PAF PAG PAF PAG PAG PAF

59 59 hemical name Group No. Foot note RIS ode Related RIS odes Diethylene glycol phenyl ether 40 DGP Diethylene glycol phthalate 34 DGL Diethylene glycol propyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether DGO PAG Diethylenetriamine 7 2 DET Diethylenetriamine pentaacetic acid, pentasodium salt solution 43 Diethylethanolamine 8 DAE Diethyl ether (IMO cargo name),seeethyl ether 41 EET Diethyl hexanol, seedecyl alcohol DAX Di-(2-ethylhexyl)adipate 34 DE Di-(2-ethylhexyl)phosphoric acid 1 1 DEP Di-(2-ethylhexyl)phthalate, seedioctyl phthalate 34 DIE DOP Diethyl phthalate 34 DP Diethyl sulfate 34 DSU Diglycidyl ether of Bisphenol A 41 BDE BPA Diglycidyl ether of Bisphenol F 41 DGF Diheptyl phthalate 34 DP Di-n-hexyl adipate 34 DA Dihexyl phthalate 34 1,4-Dihydro-9,10-dihydroxy anthracene, disodium salt solution 5 DD Diisobutylamine 7 DBU Diisobutyl carbinol (commercial cargo name),seenonyl alcohol 20 DB NNS Diisobutylene 30 DBL Diisobutyl ketone 18 DIK Diisobutyl phthalate 34 DIT Diisodecyl phthalate, seedialkyl(7-13) phthalates DID DA Diisononyl adipate 34 DNY Diisononyl phthalate, seedialkyl(7-13) phthalates DIN DA Diisooctyl phthalate 34 DIO Diisopropanolamine 8 DIP Diisopropylamine 7 DIA Diisopropylbenzene 32 DIX Diisopropyl naphthalene 32 DII N,N-Dimethylacetamide 10 DA N,N-Dimethylacetamide solution 10 DLS Dimethyl adipate 34 DLA Dimethylamine 7 DMA Dimethylamine solution 7 DMG/DMY/DM Dimethylamine salt of 4-hloro-2-methylphenoxyacetic acid DM solution, see4-hloro-2-methylphenoxyacetic acid, Dimethylamine salt solution Dimethylamine salt of 2,4-Dichlorophenoxyacetic acid solution, DAD/(DDA/DSX) see2,4-dichlorophenoxyacetic acid, Dimethylamine salt solution 2,6-Dimethylaniline 9 DMM Dimethylbenzene, seexylenes XLX Dimethylcyclicsiloxane hydrolyzate 34 N,N-Dimethylcyclohexylamine 7 DXN N,N-Dimethyldodecylamine (IMO cargo name), 7 DDY seedodecyldimethylamine Dimethylethanolamine 8 DMB Dimethylformamide 10 DMF Dimethyl furan 41 Dimethyl glutarate 34 DGT Dimethyl hydrogen phosphite 34 2 DPI Dimethyl naphthalene sulfonic acid, sodium salt solution 34 2 DNS Dimethyloctanoic acid 4 DMO Dimethyl phthalate 34 DTL Dimethylpolysiloxane,seePolydimethylsiloxane 34 DMP 2,2-Dimethylpropane-1,3-diol 20 DDI Dimethyl succinate 34 DSE Dinitrotoluene 42 DNM DTT/DNL/DNU Dinonyl phthalate, seedialkyl(7-13) phthalates DIF DA Dioctyl phthalate 34 DOP DIE 1,4-Dioxane 41 DOX Dipentene 30 DPN Diphenyl 32 DIL Diphenylamine (molten) 9 DAG DAM/LRM Diphenylamines, alkylated 7 DAJ

60 60 hemical name Group No. Foot note RIS ode Related RIS odes Diphenylamine, reaction product with 2,2,4-trimethylpentene 7 DAK Diphenyl, Diphenyl ether mixture 33 DDO DT Diphenyl ether 41 DPE Diphenyl ether, Diphenyl phenyl ether mixture 41 DOB Diphenylmethane diisocyanate 12 DPM Diphenylol propane-epichlorohydrin resins 0 1 DPR Diphenyl oxide, see asdiphenyl ether Di-n-propylamine 7 DNA Dipropylene glycol 40 DPG Dipropylene glycol butyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether DBG PAG Dipropylene glycol dibenzoate 34 DGY Dipropylene glycol methyl ether, seepoly (2-8)alkylene glycol monoalkyl(1-6) ether DPY PAG Distillates, flashed feed stocks 33 DFF Distillates, straight run 33 DSR Dithiocarbamate ester (7-35) 34 DO Ditridecyl adipate 34 Ditridecyl phthalate, seedialkyl(7-13) phthalates DTP DA Diundecyl phthalate, seedialkyl(7-13) phthalates DUP DA Dodecane 31 1 DO ALJ tert-dodecanethiol 0 2 DDL Dodecanol 20 DDN LAL Dodecene 30 DOZ DD/DOD 2-Dodecenylsuccinic acid, dipotassium salt solution 34 DSP Dodecyl alcohol (IMO cargo name),seedodecanol DDN Dodecylamine, Tetradecylamine mixture 7 DTA Dodecylbenzene,seeAlkyl(9+)benzenes 32 2 DDB AKB Dodecylbenzenesulfonic acid 0 1, 2 DSA Dodecyldimethylamine, Tetradecyldimethylamine mixture 7 DOT Dodecyl diphenyl ether disulfonate solution 43 DOS Dodecyl hydroxypropyl sulfide 0 1 DO Dodecyl methacrylate 14 1 DDM Dodecyl-Octadecyl methacrylate mixture 14 1 DOM Dodecyl-Pentadecyl methacrylate mixtures 14 1 DDP Dodecyl phenol 21 DOL Dodecyl xylene 32 2 DXY Drilling brine (containing alcium, Potassium or Sodium salts) 43 DRB Drilling brine (containing Zinc salts) 43 DZB Drilling mud (low toxicity) (if flammable or combustible) 33 DRM Drilling mud (low toxicity) (if non-flammable or non-combustible) 43 DRM Epichlorohydrin 17 1 EP Epoxy resin 18 ETBE, seeethyl tert-butyl ether EBE Ethane 31 1 ET Ethanolamine (monoethanolamine) 8 MEA 2-Ethoxyethanol, seeethylene glycol monoalkyl ethers EEO EG 2-Ethoxyethyl acetate 34 EEA Ethoxylated alcohols, 11-15, see the alcohol poylethoxylates Ethoxylated long chain (16+) alkyloxyalkanamine 8 ELA Ethoxy triglycol 40 ETG Ethyl acetate 34 ETA Ethyl acetoacetate 34 EAA Ethyl acrylate 14 1 EA Ethyl alcohol 20 2 EAL Ethylamine 7 2 EAM Ethylamine solution 7 EAN Ethyl amyl ketone 18 EAK ELK Ethylbenzene 32 ETB Ethyl butanol 20 EBT N-Ethyl-n-butylamine 7 EBA Ethyl tert-butyl ether 41 2 EBE Ethyl butyrate 34 EBR Ethyl chloride 36 EL Ethyl cyclohexane 31 1 EY N-Ethylcyclohexylamine 7 E Ethylene 30 ETL Ethyleneamine EA EMX EDA

61 61 hemical name Group No. Foot note RIS ode Related RIS odes Ethylene carbonate 34 Ethylene chlorohydrin 20 E Ethylene cyanohydrin 20 ET Ethylenediamine 7 2 EDA EMX Ethylenediaminetetraacetic acid, tetrasodium salt solution 43 EDS Ethylene dibromide 36 EDB Ethylene dichloride 36 2 ED Ethylene glycol 20 2 EGL Ethylene glycol acetate 34 EGO Ethylene glycol butyl ether, seeethylene glycol monoalkyl ethers EGM EG Ethylene glycol tert-butyl ether, seeethylene glycol monoalkyl EG ethers Ethylene glycol butyl ether acetate 34 EMA Ethylene glycol diacetate 34 EGY Ethylene glycol dibutyl ether 40 EGB Ethylene glycol ethyl ether, seeethyl glycol monoalkyl ethers EGE EG/EEO Ethylene glycol ethyl ether acetate, see2-ethoxyethyl acetate EGA EEA Ethylene glycol hexyl ether 40 EG Ethylene glycol isopropyl ether, seeethylene glycol monoalkyl EGI EG ethers Ethylene glycol methyl butyl ether, seeethylene glycol monoalkyl 40 EMB EG ethers Ethylene glycol methyl ether, seeethylene glycol monoalkyl ethers EME EG Ethylene glycol methyl ether acetate 34 EGT Ethylene glycol monoalkyl ethers 40 EG Including: Ethylene glycol butyl ether Ethylene glycol isobutyl ether Ethylene glycol tert-butyl ether Ethylene glycol ethyl ether Ethylene glycol hexyl ether Ethylene glycol methyl ether Ethylene glycol propyl ether Ethylene glycol isopropyl ether Ethylene glycol phenyl ether 40 EPE Ethylene glycol phenyl ether, Diethylene glycol phenyl ether 40 EDX mixture Ethylene glycol propyl ether, seeethylene glycol monoalkyl ethers EGP EG Ethylene glycol iso-propyl ether, seeethylene glycol monoalkyl EGI EG ethers Ethylene oxide 0 1 EOX Ethylene oxide, Propylene oxide mixture 16 1 EPM Ethylene-Propylene copolymer 30 Ethylene-Vinyl acetate copolymer emulsion 43 Ethyl ether 41 EET Ethyl-3-ethoxypropionate 34 EEP 2-Ethylhexaldehyde, seeoctyl aldehydes A OAL 2-Ethylhexanoic acid, seeoctanoic acids EO OAY 2-Ethylhexanol, seeoctanol EX OX 2-Ethylhexyl acrylate 14 1 EAI 2-Ethylhexylamine 7 EM Ethyl hexyl phthalate 34 EE Ethyl hexyl tallate 34 ET 2-Ethyl-1-(hydroxymethyl)propane-1,3-diol, 8-10 ester 34 ED Ethylidene norbornene 30 2 ENB Ethyl methacrylate 14 1 ETM N-Ethylmethylallylamine 7 EML 2-Ethyl-6-methyl-N-(1 -methyl-2-methoxyethyl)aniline 9 EEM o-ethyl phenol 21 EPL Ethyl propionate 34 EPR 2-Ethyl-3-propylacrolein 19 2 EPA Ethyl toluene 32 ETE Fatty acids (saturated, 13+),seeFatty acids (saturated, 14+) Fatty acids (saturated, 14+) 34 FAD SRA Ferric chloride solution 1 1 FS FL Ferric hydroxyethylethylenediaminetriacetic acid, trisodium salt 43 2 FX STA solution Ferric nitrate, Nitric acid solution 3 FNN

62 62 hemical name Group No. Foot note RIS ode Related RIS odes Fish solubles (water based fish meal extracts) 43 FSO Fluorosilicic acid 1 1 FSJ Formaldehyde, Methanol mixtures 19 2 MTM Formaldehyde solution 19 2 FMS Formamide 10 FAM Formic acid 4 2 FMA Fructose solution 43 Fumaric adduct of Rosin, water dispersion 43 FAR Furfural 19 FFA Furfuryl alcohol 20 2 FAL Gas oil, cracked 33 GO Gasoline blending stock, alkylates 33 GAK Gasoline blending stock, reformates 33 GRF Gasolines: Automotive (not over 4.23 grams lead per gal.) 33 GAT Aviation (not over 4.86 grams lead per gal) 33 GAV AVA asinghead (natural) 33 GS Polymer 33 GPL Straight run 33 GSR Glucose solution 43 GLU DTS Glutaraldehyde solution 19 GTA Glycerine 20 2 GR Glycerine, Dioxanedimethanol mixture 20 GDM Glycerol monooleate 20 GMO Glycerol polyalkoxylate 34 Glyceryl triacetate 34 Glycidyl ester of 10 trialkyl acetic acid (IMO cargo 34 GLT name),seeglycidyl ester of tridecyl acetic acid Gylcidyl ester of tridecylacetic acid 34 GLT Glycidyl ester of Versatic acid, seegylcidyl ester of tridecylacetic GLT acid Glycine, sodium salt solution 7 Glycol diacetate, seeethylene glycol diacetate EGY Glycolic acid solution 4 GL Glyoxal solutions 19 GOS Glyoxylic acid 4 GA Glyphosate solution (not containing surfactant) (See also 7 GIO ROUNDUP) eptadecane, seen-alkanes (10+) ALJ eptane 31 1 MX ALK (PI/PT) n-eptanoic acid 4 EP eptanol 20 TX TN eptene 30 PX TE eptyl acetate 34 PE erbicide (15-22-NO2-l), seemetolachlor MO exadecanol (cetyl alcohol), seealcohols (13+) ALY 1-exadecylnaphthalene, 1,4-bis(exadecyl)naphthalene mixture 32 exaethylene glycol, seepolyethylene glycol examethylene glycol 20 examethylenediamine 7 ME MD/M examethylenediamine solution 7 M MD/ME examethylenediamine adipate solution 43 AM examethylene diisocyanate 12 DI examethylenetetramine 7 MT examethylenetetramine solutions 7 TS examethylenimine 7 MI exane 31 2 XS ALK (IA/XA) exanoic acid 4 XO exanol 20 XN exene 30 EX XE/XT/MPN/MTN exyl acetate 34 AE SA exylene glycol 20 XG itec IT og grease, seelard ydrochloric acid 1 1 L ydrofluorosilicic acid, seefluorosilicic acid FS FSJ bis(ydrogenated tallow alkyl)methyl amines 7 TA ydrogen peroxide solutions 0 1 PN/PS/PO

63 63 hemical name Group No. Foot note RIS ode Related RIS odes 2-ydroxyethyl acrylate 14 2 AI N-(ydroxyethyl)ethylenediamine triacetic acid, trisodium salt 43 ET FX solution N,N-bis(2-ydroxyethyl) oleamide 10 OO 2-ydroxy-4-(methylthio)butanoic acid 4 BA ydroxy terminated polybutadiene (IMO cargo 20 name),seepolybutadiene, hydroxy terminated alpha-hydro-omega-ydroxytetradeca(oxytetramethylene), TO seepoly(tetramethylene ether) glycols (mw ) Icosa(oxypropane-2,3-diyl)s 20 IOP Isophorone 18 2 IP Isophorone diamine 7 IPI Isophorone diisocyanate 12 IPD Isoprene 30 IPR Isoprene concentrate (Shell) 30 IS Isopropylbenzene (cumene), seepropylbenzene PBY Jet fuels: JP-4 33 JPF JP-5 33 JPV JP-8 33 JPE Kaolin clay slurry 43 Kerosene 33 KRS Ketone residue 18 KTR Kraft black liquor 5 KPL Kraft pulping liquors (Black, Green, or White) 5 KPL Lactic acid 0 1, 2 LTA Lactonitrile solution 37 LNI Lard 34 Latex (ammonia inhibited) 30 LTX Latex, liquid synthetic 43 LLS LTX Lauric acid 34 LRA Lauryl polyglucose, seealkyl(12-14) polyglucoside solution LAP AGM (55% or less) Lecithin 34 LE Lignin liquor 43 Lignin sulfonic acid, sodium salt solution, seesodium lignosulfonate solution d-limonene, seedipentene Liquid Streptomyces solubles 43 Long chain alkaryl polyether (11-20) 41 LP Long chain alkaryl sulfonic acid (16-60) 0 1, 2 LS Long chain alkylphenate/phenol sulfide mixture 21 LPS Long chain polyetheramine in alkyl(2-4)benzenes 7 LE l-lysine solution 43 LYS Magnesium chloride solution 0 1, 2 Magnesium hydroxide slurry 5 Magnesium long chain alkaryl sulfonate (11-50) 34 MAS MSE Magnesium long chain alkyl phenate sulfide (8-20) 34 MPS Magnesium long chain alkyl salicylate (11+) 34 MLS Magnesium nonyl phenol sulfide, seemagnesium long chain alkyl MPS phenate sulfide (8-20) Magnesium sulfonate, seemagnesium long chain alkaryl sulfonate MSE MAS (11-50) Maleic anhydride 11 MLA Mercaptobenzothiazol, sodium salt solution (IMO cargo 5 SMB name),seesodium-2-mercaptobenzothiazol solution Mesityl oxide 18 2 MSO Metam sodium solution 7 MSS SMD Methacrylic acid 4 MAD Methacrylic resin in Ethylene dichloride 14 1 MRD Methacrylonitrile 15 2 MET Methane 31 1 MT 3-Methoxy-1-butanol 20 3-Methoxybutyl acetate 34 MOA N-(2-Methoxy-1-methyl ethyl)-2-ethyl-6-methyl chloroacetanilide 34 MO (IMO cargo name),seemetolachlor 1-Methoxy-2-propyl acetate 34 MPO Methoxy triglycol 40 MTG

64 64 hemical name Group No. Foot note RIS ode Related RIS odes Methyl acetate 34 MTT Methyl acetoacetate 34 MAE Methyl acetylene, Propadiene mixture 30 MAP Methyl acrylate 14 1 MAM Methyl alcohol 20 2 MAL Methylamine solutions 7 MSZ Methyl amyl acetate 34 MA Methyl amyl alcohol 20 MAA MI Methyl amyl ketone 18 MAK Methyl bromide 36 MTB Methyl butanol, see the amyl alcohols AAI Methyl butenol 20 MBL Methyl butenes (tert-amylenes), seepentene PTX Methyl tert-butyl ether 41 2 MBE Methyl butyl ketone 18 2 MBK Methylbutynol,see2-Methyl-2-hydroxy-3-butyne 20 MBY MB 3-Methyl butyraldehyde 19 Methyl butyrate 34 MBU Methyl chloride 36 MT Methylcyclohexane 31 1 MY Methylcyclopentadiene dimer 30 MK Methyl diethanolamine 8 MDE MAB Methylene chloride, seedichloromethane DM 2-Methyl-6-ethylaniline 9 MEN Methyl ethyl ketone 18 2 MEK 2-Methyl-5-ethylpyridine 9 MEP Methyl formate 34 MFM N-Methylglucamine solution 43 MG Methyl heptyl ketone 18 MK 2-Methyl-2-hydroxy-3-butyne 20 MB Methyl isoamyl ketone 18 MAK Methyl isobutyl carbinol, seemethyl amyl alcohol MI MAA Methyl isobutyl ketone 18 2 MIK Methyl methacrylate 14 1 MMM 3-Methyl-3-methoxybutanol 20 3-Methyl-3-methoxybutyl acetate 34 Methyl naphthalene 32 MNA Methylolureas 19 MUS 2-Methyl pentane 31 1 IA 2-Methyl-1-pentene, seeexene MPN EX 4-Methyl-1-pentene, seeexene MTN EX Methyl tert-pentyl ether (IMO cargo name),seetert-amyl methyl 41 AYE ether 2-Methyl-1,3-propanediol 20 MDL Methyl propyl ketone 18 MKE Methylpyridine 9 MPR/MPE/MPF N-Methyl-2-pyrrolidone 9 2 MPY Methyl salicylate 34 MES alpha-methylstyrene 30 MSR 3-(Methylthio)propionaldehyde 19 MTP Metolachlor 34 MO Milk 43 Mineral spirits 33 MNS Molasses 20 Molasses residue 0 1 Monochlorodifluoromethane 36 MF Monoethanolamine, seeethanolamine Monoisopropanolamine, seepropanolamine Morpholine 7 2 MPL Motor fuel antiknock compounds containing lead alkyls 0 1 MFA MTBE, seemethyl tert-butyl ether MBE Myrcene 30 MRE Naphtha: Aromatic 33 oal tar solvent 33 NT eavy 33 Paraffinic 33 Petroleum 33 PTN

65 65 hemical name Group No. Foot note RIS ode Related RIS odes Solvent 33 NSV Stoddard solvent 33 NSS Varnish Makers' and Painters' 33 NVM Naphthalene 32 NTM Naphthalene still residue 32 2 NSR Naphthalene sulfonic acid-formaldehyde copolymer, sodium salt 0 1 NFS solution Naphthalene sulfonic acid, sodium salt solution 34 NSA Naphthenic acid 4 NTI Naphthenic acid, sodium salt solution 43 NTS Neodecanoic acid 4 NEA NIAX POLYOL APP , 2 NXP Nitrating acid 0 1 NIA Nitric acid (70% or less) 3 ND Nitric acid (greater than 70%) 0 1 NA Nitrobenzene 42 NTB o-nitrochlorobenzene, seehloronitrobenzene NO Nitroethane 42 NTE Nitroethane, 1-Nitropropane mixtures 42 NNO o-nitrophenol 0 1, 2 NTP NIP/NP Nitropropane 42 NPM NPN/NPP Nitropropane, Nitroethane mixture 42 NNO (NNM/NNL) Nitrotoluene 42 NIT NIE/NTT/NTR Nonane 31 1 NAX ALK (NAN) Nonanoic acid 4 NNA NAI/NIN Nonanoic, Tridecanoic acid mixture 4 NAT Nonene 30 NOO NON/NNE Nonyl acetate 34 NAE Nonyl alcohol 20 2 NNS NNI/NNN/DB Nonylbenzene, seealkyl(9+)benzenes AKB Nonyl methacrylate 14 1 NMA Nonyl phenol 21 NNP Nonyl phenol poly(4+)ethoxylates 40 NPE Nonyl phenol sulfide solution, seealkyl phenol sulfide (8-40) AKS/NPS Noxious Liquid Substance, n.o.s. (NLS's) Octadecene, see the olefin or alpha-olefin entries Octadecenoamide 10 ODD Octadecenol (oleyl alcohol), seealcohols (13+) ALY Octane 31 1 OAX ALK (IOO/OAN) Octanoic acid 4 OAY OAA/EO Octanol 20 2 OX IOA/OTA/EX Octene 30 OTX OTE n-octyl acetate 34 OAF OAE Octyl alcohol, seeoctanol OX Octyl aldehyde 19 OAL IO/OLX/EA Octyl decyl adipate 34 ODA Octyl nitrate, seealkyl(7-9) nitrates ONE AKN Octyl phenol 21 Octyl phthalate, seedioctyl phthalate DOP Oil, edible: Beechnut 34 OBN VEO astor 34 OA VEO ocoa butter 34 OB VEO oconut 34 2 O VEO od liver 34 OL AFN orn 34 OO VEO ottonseed 34 OS VEO Fish 34 2 OFS AFN Groundnut 34 OGN VEO azelnut 34 ON VEO Lard 34 OLD AFN Maize 34 VEO (OO) Nutmeg butter 34 ONB VEO Olive 34 OOL VEO Palm 34 2 OPM VEO Palm kernel 34 OPO VEO Peanut 34 OPN VEO Poppy 34 OPY VEO

66 66 hemical name Group No. Foot note RIS ode Related RIS odes Poppy seed 34 VEO Raisin seed 34 ORA VEO Rapeseed 34 ORP VEO Rice bran 34 ORB VEO Safflower 34 OSF VEO Salad 34 OSL VEO Sesame 34 OSS VEO Soya bean 34 OSB VEO Sunflower seed 34 OSN VEO Tucum 34 OT VEO Vegetable 34 OVG VEO Walnut 34 OWN VEO Oil, fuel: No OON No. 1-D 33 OOD No OTW No. 2-D 33 OTD No OFR No OFV No OSX Oil, misc: Aliphatic 33 Animal 34 OMA AFN Aromatic 33 larified 33 OF oal 33 oconut oil, fatty acid methyl ester 34 OM otton seed oil, fatty acid 34 FY rude 33 OIL Diesel 33 ODS Gas, high pour 33 Gas, low pour 33 Gas, low sulfur 33 eartcut distillate 33 Lanolin 34 OLL AFN Linseed 33 OLS Lubricating 33 OLB Mineral 33 OMN Mineral seal 33 OMS Motor 33 OMT Neatsfoot 33 ONF AFN Oiticica 34 OOI Palm oil, fatty acid methyl ester 34 OPE Penetrating 33 OPT Perilla 34 OPR Pilchard 34 OPL AFN Pine 33 OPI PNL Residual 33 Road 33 ORD Rosin 33 ORN Seal 34 Soapstock 34 OIS Soybean (epoxidized) 34 EVO Sperm 33 OSP AFN Spindle 33 OSD Tall 34 OTL Tall, fatty acid 34 2 TOF Transformer 33 OTF Tung 34 OTG Turbine 33 OTB Wood 34 Olefin/Alkyl ester copolymer (molecular weight 2000+) 34 OP Olefin mixtures 30 OFX/OFY alpha-olefins (6-18) mixtures 30 OAM Olefins (13+) 30 Oleic acid 34 OLA Oleum 0 1, 2 OLM Oleyl alcohol (octadecenol), seealcohols (13+) ALY

67 67 hemical name Group No. Foot note RIS ode Related RIS odes Oleylamine 7 OLY ORIMULSION, seeasphalt emulsion ASQ Oxyalkylated alkyl phenol formaldehyde 33 Palm kernel acid oil 34 PNO Palm kernel acid oil, methyl ester 34 PNF Palm kernel oil, fatty acid, seepalm kernel acid oil PNO Palm kernel oil, fatty acid methyl ester, seepalm kernel acid oil, PNF methyl ester Palm stearin 34 PMS n-paraffins (10-20), seen-alkanes (10+) PFN ALJ Paraldehyde 19 PD Paraldehyde-Ammonia reaction product 9 PRB Pentachloroethane 36 PE Pentacosa(oxypropane-2,3-diyl)s 20 POY Pentadecanol, seealcohols (13+) PD ALY 1,3-Pentadiene 30 PDE PDN Pentaethylene glycol, seepolyethylene glycols Pentaethylene glycol methyl ether, seepoly(2-8)alkylene glycol PAG monoalkyl(1-6) ether Pentaethylenehexamine 7 PEN Pentaethylenehexamine, Tetraethylenepentamine mixture 7 PEP Pentane 31 1 PTY IPT/PTA Pentanoic acid 4 PO n-pentanoic acid, 2-Methyl butryic acid mixture 4 POJ PO Pentasodium salt of Diethylenetriamine pentaacetic acid solution, seediethylenetriamine pentaacetic acid, pentasodium salt solution Pentene 30 PTX PTE Pentyl aldehyde 19 n-pentyl propionate 34 PPE Perchloroethylene 36 2 PER TTE Petrolatum 33 PTL Phenol 21 PN 1-Phenyl-1-xylyl ethane 32 PXE Phosphate esters, alkyl(12-14)amine 7 PEA Phosphoric acid 1 1 PA Phosphorus 0 1 PPW PPR/PPB Phthalate based polyester polyol 0 1, 2 PBE Phthalic anhydride 11 PAN alpha-pinene 30 PIO PIN beta-pinene 30 PIP PIN Pine oil 33 PNL OPI Polyalkyl(18-22) acrylate in Xylene 14 1 PIX Polyalkylene glycol butyl ether, seepoly(2-8)alkylene glycol PGB PAG monoalkyl(1-6) ether Poly(2-8)alkylene glycol monoalkyl(1-6) ether 40 PAG Including: Diethylene glycol butyl ether Diethylene glycol ethyl ether Diethylene glycol n-hexyl ether Diethylene glycol methyl ether Diethylene glycol n-propyl ether Dipropylene glycol butyl ether Dipropylene glycol methyl ether Polyalkylene glycol butyl ether Polyethylene glycol monoalkyl ether Polypropylene glycol methyl ether Tetraethylene glycol methyl ether Triethylene glycol butyl ether Triethylene glycol ethyl ether Triethylene glycol methyl ether Tripropylene glycol methyl ether Poly(2-8)alkylene glycol monoalkyl(1-6) ether acetate 34 PAF Including: Diethylene glycol butyl ether acetate Diethylene glycol ethyl ether acetate Diethylene glycol methyl ether acetate Polyalkylene glycols, Polyalkylene glycol monoalkyl ethers mixtures 40 PPX

68 68 hemical name Group No. Foot note RIS ode Related RIS odes Polyalkylene oxide polyol 20 PAO Polyalkyl methacrylate (1-20) Polyalkyl(10-20)methacrylate 14 1 PMT Polyalkyl(10-18)methacrylate/Ethylene propylene copolymer 14 1 PEM mixture Polyaluminum chloride solution 1 1 Polybutadiene, hydroxyl terminated 20 Polybutene 30 PLB Polybutenyl succinimide 10 PBS Poly(2+)cyclic aromatics 32 PA Polydimethylsiloxane 34 Polyether (molecular weight 2000+) 41 PYR Polyethylene glycol 40 Polyethylene glycol dimethyl ether 40 Polyethylene glycol monoalkyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether Polyethylene polyamines 7 2 PEB Polyferric sulfate solution 34 PSS Polyglycerine, Sodium salts solution (containing less than 3% Sodium hydroxide) 20 2 PGT Polyglycerol 20 GR Polyisobutenamine in aliphatic (10-14) solvent 7 PIB Polyisobutenyl anhydride adduct 11 Poly(4+)isobutylene 30 Polymethylene polyphenyl isocyanate 12 PPI Polymethylsiloxane 34 Polyolefin (molecular weight 300+) 30 Polyolefin amide alkeneamine (17+) 33 PO Polyolefin amide alkeneamine (28+) 33 POD Polyolefin amide alkeneamine borate (28-250) 33 PAB Polyolefin amide alkeneamine/molybdenum oxysulfide mixture 7 Polyolefin amide alkeneamine polyol 20 PAP Poly(17+)olefin amine 7 POG Polyolefinamine (28-250) 33 POM Polyolefinamine in alkyl(2-4)benzenes 32 POF Polyolefin aminoester salt 34 PAE Polyolefin anhydride 11 PAR Polyolefin ester (28-250) 34 POS Polyolefin phenolic amine (28-250) 7 PP Polyolefin phosphorosulfide, barium derivative (28-250) 34 PPS Poly(20)oxyethylene sorbitan monooleate 34 PSM Poly(5+)propylene 30 PLQ PLP Polypropylene glycol 40 PG Polypropylene glycol methyl ether, seepropylene glycol monoalkyl ether PGM PGE Polysiloxane 34 DMP Poly(tetramethylene ether) glycols (mw ) (alpha-hydroomega-ydroxytetradeca(oxytetramethylene)) 40 TO Polytetramethylene ether glycol 40 Potassium chloride solution 43 PS (DRB) Potassium formate solution 34 PFR Potassium hydroxide solution (IMO cargo name),seeaustic potash solution 5 2 PS Potassium oleate 34 POE Potassium salt of polyolefin acid 34 Potassium thiosulfate solution 43 PTF Propane 31 1 PRP Propanolamine 8 PAX MPA/PLA Propionaldehyde 19 PAD Propionic acid 4 PNA Propionic anhydride 11 PA Propionitrile 37 PN n-propoxypropanol, seepropylene glycol monoalkyl ether PXP PGE Propyl acetate 34 IA/PAT Propyl alcohol 20 2 IPA/PAL Propylamine 7 IPP/PRA iso-propylamine solution 7 IPO/IPQ Propylbenzene 32 2 PBY PBZ/UM PEE PAG

69 69 hemical name Group No. Foot note RIS ode Related RIS odes n-propyl chloride 36 PR iso-propylcyclohexane 31 1 IPX Propylene 30 PPL Propylene-butylene copolymer 30 PBP Propylene carbonate 34 Propylene dimer 30 PDR Propylene glycol 20 2 PPG Propylene glycol n-butyl ether, seepropylene glycol monoalkyl PGD PGE ether Propylene glycol ethyl ether, seepropylene glycol monoalkyl ether PGY PGE Propylene glycol methyl ether, seepropylene glycol monoalkyl ether PME PGE Propylene glycol methyl ether acetate 34 PGN Propylene glycol monoalkyl ether 40 PGE Including: n-propoxypropanol Propylene glycol n-butyl ether Propylene glycol ethyl ether Propylene glycol methyl ether Propylene glycol propyl ether Propylene glycol phenyl ether 40 PGP Propylene glycol propyl ether, seepropylene glycol monoalkyl ether PGE Propylene oxide 16 1 POX Propylene, Propane, MAPP gas mixture 30 2 PPM Propylene tetramer 30 PTT Propylene trimer 30 PTR Propyl ether 41 IPE/PRE Pseudocumene, seetrimethylbenzene TME/TRE Pyridine 9 PRD Pyridine bases, seeparaldehyde-ammonia reaction product PRB Roehm monomer RMN Rosin oil 33 ORN Rosin soap (disproportionated) solution 43 RSP ROUNDUP (See also Glyphosate solution) 7 RUP Rum, seealcoholic beverages SAP SON Sewage sludge 43 Silica slurry 43 Sludge, treated 43 Sodium acetate, Glycol, Water mixture (not containing Sodium 34 2 SAO SAP hydroxide) Sodium acetate, Glycol, Water mixture (containing Sodium 5 SAP SAO hydroxide) Sodium acetate solution 34 SAN AKP Sodium alkyl sulfonate solution 43 SSU Sodium alkyl (14-17) sulfonates 60-65% solution (IMO cargo 34 AKA name),seealkane (14-17) sulfonic acid, sodium salt solution Sodium aluminate solution 5 SAU Sodium aluminosillicate slurry 34 Sodium benzoate solution 34 SBN Sodium borohydride, Sodium hydroxide solution 5 SBX SB/SBI Sodium carbonate solutions 5 SE Sodium chlorate solution 0 1, 2 SDD SD Sodium cyanide solution 5 SS SN Sodium dichromate solution 0 1, 2 SDL SR Sodium dimethyl naphthalene sulfonate solution, seedimethyl DNS naphthalene sulfonic acid, sodium salt solution Sodium hydrogen sulfide, Sodium carbonate solution 0 1, 2 SSS Sodium hydrogen sulfite solution 43 SX Sodium hydrosulfide solution 5 2 SR Sodium hydrosulfide, Ammonium sulfide solution 5 2 SSA Sodium hydroxide solution (IMO cargo name),seeaustic soda 5 2 SS solution Sodium hypochlorite solution 5 SP/SQ/(S) Sodium lignosulfonate solution,see alsolignin liquor 43 Sodium long chain alkyl salicylate (13+) 34 SLS Sodium 2-mercaptobenzothiazol solution 5 SMB Sodium N-methyl dithio carbamate solution, seemetam sodium MSS

70 70 hemical name Group No. Foot note RIS ode Related RIS odes solution Sodium naphthalene sulfonate solution, seenaphthalene sulfonic SNS NSA acid, sodium salt solution Sodium naphthenate solution, seenaphthenic acid, sodium salt NTS solution Sodium nitrite solution 5 SNI SNT Sodium petroleum sulfonate 33 SPS Sodium polyacrylate solution 43 2 Sodium salt of Ferric hydroxyethylethylenediaminetriacetic acid STA FX solution, seeferric hydroxyethylethylenediaminetriacetic acid, trisodium salt solution Sodium silicate solution 43 2 SSN SS Sodium sulfide, ydrosulfide solution 0 1, 2 SS/SSI/SSJ Sodium sulfide solution 43 SDR Sodium sulfite solution 43 SUP SUS Sodium tartrates, Sodium succinates solution 43 STM Sodium thiocyanate solution 0 1, 2 STS SY Sorbitol solutions 20 SBT Soyabean oil (expoxidized) 34 OS/EVO Stearic acid, seefatty acids (saturated, 14+) SRA FAD Stearyl alcohol 20 Styrene 30 STY STX Styrene monomer 30 STY STX Sulfohydrocarbon (3-88) 33 SFO Sulfohydrocarbon, long chain (18+) alkylamine mixture 7 SFX Sulfolane 39 SFL Sulfonated polyacrylate solutions 43 2 Sulfur 0 1 SXX Sulfuric acid 2 2 SFA Sulfuric acid, spent 2 SA Sulfurized fat (14-20) 33 SFT Sulfurized polyolefinamide alkene(28-250) amine 33 SPO Tall oil 34 OTL Tall oil fatty acid (Resin acids less than 20%) 34 2 TOF Tall oil fatty acid, barium salt 0 1, 2 TOB Tall oil soap (disproportionated) solution 43 TOS Tallow 34 2 TLO Tallow fatty acid 34 2 TFD Tallow fatty alcohol, seealcohols (13+) TFA ALY Tallow nitrile 37 TAN TAME, seetert-amyl methyl ether AYE 1,1,2,2-Tetrachloroethane 36 TE Tetrachloroethylene, seeperchloroethylene TTE PER Tetradecanol, seealcohols (13+) TTN ALY Tetradecene, see the olefins entries TTD Tetradecylbenzene,seeAlkyl(9+) benzenes 32 TDB AKB Tetraethylene glycol 40 TTG Tetraethylene glycol methyl ether, seepoly(2-8)alkylene glycol PAG monoalkyl(1-6) ether Tetraethylenepentamine 7 2 TTP Tetrahydrofuran 41 TF Tetrahydronaphthalene 32 TN 1,2,3,5-Tetramethylbenzene, seetetramethylbenzene TTB TT Tetramethylbenzene 32 TT TTB Tetrapropylbenzene, seealkyl(9+)benzenes AKB Tetrasodium salt of EDTA solution, seeethylenediaminetetraacetic EDS acid, tetrasodium salt solution Titanium dioxide slurry 43 TDS Titanium tetrachloride 2 TTT Toluene 32 TOL Toluenediamine 9 TDA Toluene diisocyanate 12 TDI o-toluidine 9 TLI Triarylphosphate, seetriisopropylated phenyl phosphates TRA TPL Tributyl phosphate 34 TBP 1,2,4-Trichlorobenzene 36 TB 1,1,1-Trichloroethane 36 2 TE 1,1,2-Trichloroethane 36 TM

71 71 hemical name Group No. Foot note RIS ode Related RIS odes Trichloroethylene 36 2 TL 1,2,3-Trichloropropane 36 2 TN 1,1,2-Trichloro-1,2,2-trifluoroethane 36 TTF Tricresyl phosphate 34 TO/TP Tridecane, seen-alkanes (10+) TRD ALJ Tridecanoic acid 34 TDO Tridecanol, seealcohols (13+) TDN ALY Tridecene, seeolefins (13+) TD Tridecyl acetate 34 TAE Tridecylbenzene,seeAlkyl(9+) benzenes 32 2 TRB AKB Triethanolamine 8 2 TEA Triethylamine 7 TEN Triethylbenzene 32 2 TEB Triethylene glycol 40 TEG Triethylene glycol butyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether Triethylene glycol butyl ether mixture 40 Triethylene glycol dibenzoate 34 TGB Triethylene glycol di-(2-ethylbutyrate) 34 TGD Triethylene glycol ether mixture 40 Triethylene glycol ethyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether Triethylene glycol methyl ether, seepoly(2-8)alkylene glycol TGY monoalkyl(1-6) ether Triethylenetetramine 7 2 TET Triethyl phosphate 34 TPS Triethyl phosphite 34 2 TPI Triisobutylene 30 TIB Triisooctyl trimellitate 34 Triisopropanolamine 8 TIP Triisopropanolamine salt of 2,4-Dichlorophenoxyacetic acid solution, see2,4-dichlorophenoxyacetic acid, Triisopropanolamine salt solution Triisopropylated phenyl phosphates 34 TPL Trimethylacetic acid 4 TAA Trimethylamine solution 7 TMT Trimethylbenzene 32 2 TRE TME/TMB/TMD Trimethylhexamethylenediamine (2,2,4- and 2,4,4-) 7 TA Trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4-) 12 TI Trimethyl nonanol, seedodecanol Trimethylol propane polyethoxylate 20 TPR 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate 34 TMQ 2,2,4-Trimethyl-1,3-pentanediol-1-isobutyrate 34 TMP 2,2,4-Trimethyl-3-pentanol-1-isobutyrate 34 Trimethyl phosphite 34 2 TPP 1,3,5-Trioxane 41 2 TRO Triphenylborane, austic soda solution 5 TPB Tripropylene, seepropylene trimer Tripropylene glycol 40 TG Tripropylene glycol methyl ether, seepoly(2-8)alkylene glycol monoalkyl(1-6) ether TGM Trisodium nitrilotriacetate 34 Trisodium phosphate solution 5 TSP Trisodium salt of N-(ydroxyethyl)ethylenediaminetriacetic acid solution, seen-(ydroxyethyl)ethylenediaminetriacetic acid, trisodium salt solution Trixylyl phosphate (IMO cargo name),seetrixylenyl phosphate 34 TRP Trixylenyl phosphate 34 TRP Turpentine 30 TPT Ucarsol R Solvent 302 SG 8 US Undecanoic acid 4 UDA Undecanol, seeundecyl alcohol UND Undecene 30 UD Undecyl alcohol 20 UND Undecylbenzene,seeAlkyl(9+) benzenes UDB AKB Urea, Ammonium mono- and di-hydrogen phosphate, Potassium 0 1 UPX chloride solution Urea, Ammonium nitrate solution (containing Ammonia) 6 UAS TGE PAG PAG PAG DTI DDN PTR PAG ET

72 72 hemical name Group No. Foot note RIS ode Related RIS odes Urea, Ammonium nitrate solution (not containing Ammonia) 43 UAT ANU Urea, Ammonium phosphate solution 43 UAP Urea solution 43 URE Valeraldehyde 19 VAK IVA/VAL Vanillin black liquor 5 VBL Vegetable oils, n.o.s. 34 VEO Including: Beechnut oil astor oil ocoa butter oconut oil orn oil ottonseed oil Groundnut oil azelnut oil Linseed oil Nutmeg butter Oiticica oil Olive oil Palm kernel oil Palm oil Peel oil (oranges and lemons) Perilla oil Poppy oil Raisin seed oil Rapeseed oil Rice bran oil Safflower oil Salad oil Sesame oil Soya bean oil Sunflower seed oil Tucum oil Tung oil Walnut oil Vegetable acid oils and distillates, n.o.s. 34 VAO Including: orn acid oil ottonseed acid oil Dark mixed acid oil Groundnut acid oil Mixed acid oil Mixed general acid oil Mixed hard acid oil Mixed soft acid oil Rapeseed acid oil Safflower acid oil Soya acid oil Sunflower seed acid oil Vegetable protein solution 43 Vinyl acetate 13 1 VAM Vinyl chloride 35 VM Vinyl ethyl ether 13 1 VEE Vinylidene chloride 35 VI Vinyl neodecanate 13 1 VND Vinyltoluene 13 1 VNT Water 43 Waxes: WAX andelilla 34 WD arnauba 34 WA Paraffin 31 1 WPF Petroleum 33 Wine, seealcoholic beverages White spirit (low (15-20%) aromatic) 33 WSL WSP Xylene 32 XLX XLM/XLO/XLP Xylenes, Ethylbenzene mixture 32 XEB Xylenols 21 XYL Zinc alkaryl dithiophosphate (7-16) 34 ZAD

73 73 hemical name Group No. Foot note RIS ode Related RIS odes Zinc alkenyl carboxamide 10 ZAA Zinc alkyl dithiophosphate (3-14) 34 ZAP Zinc bromide, alcium bromide solution, seedrilling brine (containing Zinc salts) DZB 1. Because of very high reactivity or unusual conditions of carriage or potential compatibility problems, this commodity is not assigned to a specific group in the ompatibility hart. For additional compatibility information, contact ommandant (G-ENG-5), Attn: azardous Materials Division, U.S. oast Guard Stop 7509, 2703 Martin Luther King Jr. Avenue SE., Washington, D Telephone or hazmatstandards@uscg.mil. 2. See Appendix I Exceptions to the hart. [USG , 65 FR 67162, Nov. 8, 2000, as amended by USG , 71 FR 55746, Sept. 25, 2006; USG , 73 FR 56510, Sept. 29, 2008; USG , 74 FR 49236, Sept. 25, 2009; USG , 75 FR 60003, Sept. 29, 2010; USG , 77 FR 59783, Oct. 1, 2012; USG , 78 FR 60155, Sept. 30, 2013] Table II to Part 150 Grouping of argoes 0. Unassigned argoes Acetone cyanohydrin 1 2 Alkylbenzenesulfonic acid 1 2 Aluminium chloride, ydrochloric acid solution 1 Ammonium hydrogen phosphate solution 1 Ammonium nitrate solution 1 Ammonium thiocyanate, Ammonium thiosulfate solution 1 Benzenesulfonyl chloride 1 2 gamma-butyrolactone 1 2 hlorine 1 hlorosulfonic acid 1 Decyloxytetrahydro-thiophene dioxide 2 tert-dodecanethiol 2 2,4-Dichlorophenoxyacetic acid, Dimethylamine salt solution 1 2 Dimethylamine salt of 2,4- Dichlorophenoxyacetic acid solution 1 2 Diphenylol propane-epichlorohydrin resins 1 Dodecylbenzenesulfonic acid 1 2 Dodecyl hydroxypropyl sulfide 2 Ethylene oxide 1 ydrogen peroxide solutions 1 Lactic acid 2 Long chain alkaryl sulfonic acid (16-60) 2 Magnesium chloride solution 1 2 Molasses residue 1 Motor fuel antiknock compounds containing Lead alkyls 1 Naphthalene sulfonic acidformaldehyde copolymer, sodium salt solution 1 NIAX POLYOL APP Nitrating acid 1 Nitric acid (greater than 70%) 1 o-nitrophenol 1 2 Noxious Liquid Substance, n.o.s. (NLS's) 1 Oleum 1 2 Phosphorus 1 Phthalate based polyester polyol 2 SAP Sodium chlorate solution 1 2 Sodium dichromate solution 1 2 Sodium hydrogen sulfide, Sodium carbonate solution 1 2 Sodium sulfide, ydrosulfide solution 1 2 Sodium thiocyanate solution 1 2 Sulfur 1 Tall oil fatty acid, barium salt 2 Urea, Ammonium mono- and dihydrogen phosphate, Potassium chloride solution 1. Non-Oxidizing Mineral Acids Di-(2-ethylhexyl)phosphoric acid Ferric chloride solution Fluorosilicic acid ydrochloric acid Phosphoric acid Polyaluminum chloride solution 2. Sulfuric Acids Sulfuric acid 2 Sulfuric acid, spent Titanium tetrachloride 3. Nitric Acid Ferric nitrate, Nitric acid solution Nitric acid (70% or less) 4. Organic Acids Acetic acid 2 Acrylic acid 2 Butyric acid ashew nut shell oil (untreated) itric acid hloroacetic acid solution hloropropionic acid Decanoic acid 2,2-Dichloropropionic acid 2,2-Dimethyloctanoic acid 2-Ethylhexanoic acid Formic acid 2 Glycolic acid Glyoxylic acid n-eptanoic acid exanoic acid 2-ydroxy-4-(methylthio)butanoic acid Methacrylic acid Naphthenic acid Neodecanoic acid Nonanoic acid Nonanoic, Tridecanoic acid mixture Octanoic acid n-pentanoic acid, 2-Methyl butryic acid mixture Pentanoic acid Propionic acid Trimethylacetic acid Undecanoic acid 5. austics Ammonium sulfide solution alcium hypochlorite solutions austic potash solution 2 austic soda solution 2 resylate spent caustic resylic acid, sodium salt solution Kraft black liquor Kraft pulping liquors Mercaptobenzothiazol, sodium salt solution Potassium hydroxide solution 2 Sodium acetate, Glycol, Water mixture (containing Sodium hydroxide) Sodium aluminate solution Sodium borohydride, Sodium hydroxide solution Sodium carbonate solutions Sodium cyanide solution Sodium hydrosulfide solution 2 Sodium hydrosulfide, Ammonium sulfide solution 2 Sodium hydroxide solution 2 Sodium hypochlorite solution Sodium 2-mercaptobenzothiazol solution Sodium naphthenate solution Sodium nitrite solution Triphenylborane, austic soda solution Trisodium phosphate solution Vanillin black liquor 6. Ammonia Ammonia, anhydrous Ammonia, aqueous Ammonium hydroxide (28% or less Ammonia)

74 74 Ammonium nitrate, Urea solution (containing Ammonia) Urea, Ammonium nitrate solution (containing Ammonia) 7. Aliphatic Amines N-Aminoethylpiperazine Butylamine yclohexylamine Dibutylamine Diethylamine 2 Diethylenetriamine 2 Diisobutylamine Diisopropylamine Dimethylamine Dimethylamine solution N,N-Dimethylcyclohexylamine N,N-Dimethyldodecylamine Di-n-propylamine Diphenylamine, reaction product with 2,2,4-Trimethylpentene Diphenylamines, alkylated Dodecylamine, Tetradecylamine mixture 2 Dodecyldimethylamine, Tetradecyldimethylamine mixture Ethylamine 2 Ethylamine solution Ethyleneamine EA N-Ethyl-n-butylamine N-Ethyl cyclohexylamine Ethylenediamine 2 2-Ethyl hexylamine N-Ethylmethylallylamine Glyphosate solution (not containing surfactant) examethylenediamine examethylenediamine solution examethylenetetramine examethylenetetramine solutions examethylenimine itec 321 bis-(ydrogenated tallow alkyl)methyl amines Isophorone diamine Long chain polyetheramine in alkyl(2 4)benzenes Metam sodium solution Methylamine solutions Morpholine 2 Oleylamine Pentaethylenehexamine Pentaethylenehexamine, Tetraethylenepentamine mixture Phosphate esters, alkyl (12 14) amine Polyethylene polyamines 2 Polyolefin amide alkeneamine (28+) Polyisobutenamine in aliphatic (10 14) solvent Poly (17+) olefin amine Polyolefin amide alkeneamine/molybdenum oxysulfide mixture Propanil, Mesityl oxide, Isophorone mixture Propylamine iso-propylamine solution Roundup Sulfohydrocarbon, long chain (18+) alkylamine mixture Tetraethylenepentamine 2 Triethylamine Triethylenetetramine 2 Trimethylamine solution Trimethylhexamethylene diamine (2,2,4- and 2,4,4-) 8. Alkanolamines 2-(2-Aminoethoxy)ethanol Aminoethyldiethanolamine, Aminoethylethanolamine solution Aminoethylethanolamine 2-Amino-2-methyl-1-propanol Diethanolamine Diethylaminoethanol Diethylethanolamine Diisopropanolamine Dimethylethanolamine Ethanolamine Ethoxylated long chain (16+) alkyloxyalkanamine Methyl diethanolamine Propanolamine Triethanolamine 2 Triisopropanolamine Ucarsol R Solvent 302 SG 9. Aromatic Amines Alkyl (8 9) phenylamine in aromatic solvents Aniline alcium long chain alkyl phenolic amine (8 40) 4-hloro-2-methylphenoxyacetic acid, Dimethylamine salt solution Dialkyl (8 9) diphenylamines 2,6-Diethylaniline Dimethylamine salt of 4-hloro-2- methylphenoxyacetic acid solution 2,6-Dimethylaniline Diphenylamine 2-Ethyl-6-methyl-N-(1 -methyl-2- methoxyethyl)aniline 2-Methyl-6-ethyl aniline 2-Methyl-5-ethyl pyridine Methyl pyridine 3-Methylpyridine N-Methyl-2-pyrrolidone 2 Paraldehyde-Ammonia reaction product Pyridine Pyridine bases Toluenediamine p-toluidine 10. Amides Acetochlor Acrylamide solution Alkenyl(11+)amide N,N-Dimethylacetamide N,N-Dimethylacetamide solution Dimethylformamide Formamide N,N-bis(2-ydroxyethyl) oleamide Octadecenoamide Zinc alkenyl carboxamide 11. Organic Anhydrides Acetic anhydride Alkenylsuccinic anhydride Maleic anhydride Phthalic anhydride Polyisobutenyl anhydride adduct Polyolefin anhydride Propionic anhydride 12. Isocyanates Diphenylmethane diisocyanate examethylene diisocyanate Isophorone diisocyanate Polymethylene polyphenyl isocyanate Toluene diisocyanate Trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4-) 13. Vinyl Acetate Vinyl acetate Vinyl ethyl ether Vinyl neodecanate Vinyl toluene 14. Acrylates Butyl acrylate Butyl methacrylate Butyl methacrylate, Decyl methacrylate, etyl-eicosyl methacrylate mixture etyl-eicosyl methacrylate mixture Decyl acrylate Dodecyl methacrylate Dodecyl-Octadecyl methacrylate mixture Dodecyl-Pentadecyl methacrylate mixture Ethyl acrylate 2-Ethylhexyl acrylate Ethyl methacrylate 2-ydroxyethyl acrylate 2 Methacrylic resin in Ethylene dichloride Methyl acrylate Methyl methacrylate Nonyl methacrylate Polyalkyl(18-22) acrylate in Xylene Polyalkyl (10 18) methacrylate/ethylene Polyalkyl (10 20) methacrylate Propylene copolymer mixture

75 75 Roehm monomer Substituted Allyls Acrylonitrile 2 Allyl alcohol 2 Allyl chloride 1,3-Dichloropropene Dichloropropene, Dichloropropane mixtures Methacrylonitrile 16. Alkylene Oxides Butylene oxide Ethylene oxide, Propylene oxide mixtures Propylene oxide 17. Epichlorohydrin hlorohydrins Epichlorohydrin 18. Ketones Acetone 2 Acetophenone Amyl methyl ketone Butyl heptyl ketone amphor oil 1-(4-hlorophenyl)-4,4-dimethyl pentan-3-one 2 yclohexanone yclohexanone, yclohexanol mixtures 2 Diisobutyl ketone Ethyl amyl ketone Epoxy resin Ketone residue Isophorone 2 Mesityl oxide 2 Methyl amyl ketone Methyl butyl ketone Methyl butyl ketone Methyl ethyl ketone 2 Methyl heptyl ketone Methyl isoamyl ketone Methyl isobutyl ketone 2 Methyl propyl ketone Trifluralin in Xylene 19. Aldehydes Acetaldehyde Acrolein 2 Butyraldehyde rotonaldehyde 2 Decaldehyde Ethylhexaldehyde 2-Ethyl-3-propylacrolein 2 Formaldehyde, Methanol mixtures 2 Formaldehyde solution 2 Furfural Glutaraldehyde solution Glyoxal solutions 3-Methyl butyraldehyde Methylolureas 3-(Methylthio)propionaldehyde Octyl aldehyde Paraldehyde Pentyl aldehyde Propionaldehyde Valeraldehyde 20. Alcohols, Glycols Acrylonitrile-Styrene copolymer dispersion in Polyether polyol Alcoholic beverages Alcohol polyethoxylates Alcohol polyethoxylates, secondary Alcohols (13+) Amyl alcohol Behenyl alcohol Brake fluid base mixtures 1,4-Butanediol Butyl alcohol 2 Butylene glycol 2 etyl-stearyl alcohol holine chloride solutions yclohexanol Decyl alcohol 2 Diacetone alcohol 2 Diethyl hexanol Diisobutyl carbinol 2,2-Dimethylpropane-1,3-diol Dodecanol Dodecyl alcohol Ethoxylated alcohols, Ethoxyethanol Ethyl alcohol 2 Ethyl butanol Ethylene chlorohydrin Ethylene cyanohydrin Ethylene glycol 2 2-Ethylhexanol Furfuryl alcohol 2 Glycerine 2 Glycerine, Dioxanedimethanol mixture Glycerol monooleate eptanol examethylene glycol exanol exylene glycol ydroxy terminated polybutadiene Icosa(oxypropane-2,3-diyl)s Lauryl polyglucose (50% or less) 3-Methoxy-1-butanol Methyl alcohol 2 Methyl amyl alcohol Methyl butenol Methylbutynol 2-Methyl-2-hydroxy-3-butyne Methyl isobutyl carbinol 3-Methyl-3-methoxybutanol 2-Methyl-1,3-propanediol Molasses Nonyl alcohol 2 Octanol 2 Octyl alcohol 2 Penacosa(oxypropane-2,3-diyl)s Pentadecanol Polyalkylene oxide polyol Polybutadiene, hydroxy terminated Polyglycerol Polyglycerine, Sodium salts solution (containing less than 3% Sodium hydroxide) 2 Polyolefin amide alkeneamine polyol Propyl alcohol 2 Propylene glycol 2 Rum Sorbitol solutions Stearyl alcohol Tallow fatty alcohol Tetradecanol Tridecanol Trimethyl nonanol Trimethylol propane polyethoxylate Undecanol Undecyl alcohol 21. Phenols, resols Benzyl alcohol arbolic oil reosote 2 resols resylic acid resylic acid dephenolized resylic acid, tar Dibutylphenols 2,4-Dichlorophenol Dodecyl phenol o-ethylphenol Long chain alkylphenate/phenol sulfide mixture Nonyl phenol Octyl phenol Phenol Xylenols 22. aprolactam Solutions aprolactam solution Unassigned 30. Olefins Amylene Aryl polyolefin (11 50) Butadiene Butadiene, Butylene mixtures (cont. Acetylenes) Butene Butene oligomer Butylene 1,5,9-yclododecatriene 1,3-yclopentadiene dimer yclopentadiene, Styrene, Benzene mixture yclopentene Decene Dicyclopentadiene Diisobutylene Dipentene Dodecene Ethylene

76 76 Ethylene-Propylene copolymer Ethylidene norbornene 2 1-eptene exene Isoprene Isoprene concentrate (Shell) Latex (ammonia (1% or less) inhibited) Methyl acetylene, Propadiene mixture Methyl butene Methylcyclopentadiene dimer 2-Methyl-1-pentene 4-Methyl-1-pentene alpha-methyl styrene Myrcene Nonene 1-Octadecene Octene Olefin mixtures alpha-olefins (6-18) mixtures alpha-olefins (13+) 1,3-Pentadiene Pentene alpha-pinene beta-pinene Polybutene Poly(4+)isobutylene Polyolefin (molecular weight 300+) Polypropylene Poly(5+)propylene Propylene Propylene-butylene copolymer Propylene dimer Propylene, Propane, MAPP gas mixture Propylene tetramer Propylene trimer Styrene monomer Tetradecene Tridecene Triisobutylene Tripropylene Turpentine Undecene 31. Paraffins Alkanes (6 9) n-alkanes (10+) iso- & cyclo-alkanes (10 11) iso- & cyclo-alkanes (12+) Butane ycloheptane yclohexane yclopentane Decane Dodecane Ethane Ethyl cyclohexane eptane exane 2 Methane Methylcyclohexane 2-Methyl pentane Nonane Octane Pentane Propane iso-propylcyclohexane Tridecane Waxes: Paraffin 32. Aromatic ydrocarbons Alkyl(3 4)benzenes Alkyl(5 8)benzenes Alkyl(9+)benzenes Alkyl acrylate-vinyl pyridine copolymer in Toluene Alkylbenzene, Alkylindane, Alkylindene mixture (each 12 17) Benzene Benzene hydrocarbon mixtures (having 10% Benzene or more) Benzene, Toluene, Xylene mixtures Butylbenzene Butyl phenol, Formaldehyde resin in Xylene Butyl toluene umene ymene Decylbenzene Dialkyl(10-14) benzenes Diethylbenzene Diisopropylbenzene Diisopropyl naphthalene Diphenyl Dodecylbenzene Dodecyl xylene Ethylbenzene Ethyl toluene 1-exadecylnaphthalene, 1,4- bis(exadecyl) Isopropylbenzene Methyl naphthalene Naphthalene Naphthalene mixture Naphthalene still residue 1-Phenyl-1-xylyl ethane Poly(2+)cyclic aromatics Polyolefin amine in alkylbenzenes (2 4) Propylbenzene Pseudocumene 9 Resinfeed (DSM) 2 Tetradecylbenzene Tetrahydronaphthalene 1,2,3,5-Tetramethylbenzene Toluene Tridecylbenzene Triethylbenzene Trimethylbenzene Undecylbenzene Xylene Xylenes, Ethylbenzene mixture 33. Miscellaneous ydrocarbon Mixtures Alachlor Alkylbenzenesulfonic acid, sodium salt solutions Alkyl dithiothiadiazole (6 24) Asphalt blending stocks, roofers flux Asphalt blending stocks, straight run residue Asphalt emulsion Aviation alkylates alcuim sulfonate, alcium carbonate, ydrocarbon solvent mixture oal tar oal tar distillate oal tar, high temperature oal tar pitch Decahydronaphthalene Degummed 9 (DOW) Diphenyl, Diphenyl ether Distillates, flashed feed stocks Distillates, straight run Drilling mud (low toxicity) ( if flammable or combustible ) Gas oil, cracked Gasoline blending stock, alkylates Gasoline blending stock, reformates Gasolines: Automotive ( not over 4.23 grams lead per gal. ) Aviation ( not over 4.86 grams lead per gal. ) asinghead ( natural ) Polymer Straight run Jet Fuels: JP-4 JP-5 JP-8 Kerosene Mineral spirits Naphtha: oal tar solvent Petroleum Solvent Stoddard solvent Varnish Makers' and Painters' Oil, fuel: No. 1 No. 1-D No. 2 No. 2-D No. 4 No. 5 No. 6 Oil, misc: Aliphatic Aromatic larified oal rude Diesel Gas, high pour eartcut distillate Linseed

77 77 Lubricating Mineral Mineral seal Motor Neatsfoot Penetrating Pine Rosin Sperm Spindle Turbine Residual Road Transformer Oxyalkylated alkyl phenol formaldehyde Petrolatum Pine oil Polyolefin amine (28 250) Polyolefin amide alkeneamine (17+) Polyolefin amide alkeneamine borate (28 250) Sodium petroleum sulfonate Sulfohydrocarbon (3 88) Waxes: Petroleum Sulfurized fat (14 20) Sulfurized polyolefinamide alkeneamines (28 250) White spirit (low (15-20%) aromatic) 34. Esters Alkane (14 17) sulfonic acid, sodium salt solution Alkyl(8+)amine, Alkenyl (12+) acid ester mixture Alkyl ester copolymer (6 18) Alkyl(7 9) nitrates 2 Alkyl (8 40) phenol sulfide Alkyl (10 20, saturated and unsaturated) phosphite Alkyl sulfonic acid ester of phenol Alkylaryl phosphate mixtures (more than 40% Amyl acetate Animal and Fish oils, n.o.s. Animal and Fish acid oils and distillates, n.o.s. Barium long chain alkaryl (11 50) sulfonate Barium long chain alkyl(8 14)phenate sulfide Benzene tricarboxylic acid trioctyl ester Benzyl acetate Butyl acetate Butyl benzyl phthalate n-butyl butyrate Butyl formate iso-butyl isobutyrate n-butyl propionate alcium alkyl(9)phenol sulfide, polyolefin phosphorosulfide mixture alcium long chain alkaryl sulfonate (11 50) alcium long chain alkyl phenate sulfide (8 40) alcium long chain alkyl phenates alcium long chain alkyl salicylate (13+) alcium nitrate, Magnesium nitrate, Potassium chloride solution alcium nitrate solution obalt naphthenate in solvent naphtha oconut oil, fatty acid opper salt of long chain alkanoic acids ottonseed oil, fatty acid yclohexyl acetate Decyl acetate Dialkyl(7-13) phthalates Dibutyl hydrogen phosphonate Dibutyl phthalate Diethylene glycol butyl ether acetate Diethylene glycol dibenzoate Diethylene glycol ethyl ether acetate Diethylene glycol methyl ether acetate Diethylene glycol phthalate Di-(2-ethylhexyl)adipate Di-(2-ethylhexyl)phthalate Diethyl phthalate Diethyl sulfate Diheptyl phthalate Dihexyl phthalate Di-n-hexyl adipate Diisobutyl phthalate Diisodecyl phthalate Diisononyl adipate Diisononyl phthalate Diisooctyl phthalate Dimethyl adipate Dimethylcyclicsiloxane hydrolyzate Dimethyl glutarate Dimethyl hydrogen phosphite 2 Dimethyl naphthalene sulfonic acid, sodium salt solution 2 Dimethyl phthalate Dimethyl polysiloxane Dimethyl succinate Dinonyl phthalate Dioctyl phthalate Diphenyl tolyl phosphate, less than 0.02% ortho-isomer) Dipropylene glycol dibenzoate Dithiocarbamate ester (7 35) Ditridecyl adipate Ditridecyl phthalate 2-Dodecenylsuccinic acid, dipotassium salt solution Diundecyl phthalate 2-Ethoxyethyl acetate Ethyl acetate Ethyl acetoacetate Ethyl butyrate Ethylene carbonate Ethylene glycol acetate Ethylene glycol butyl ether acetate Ethylene glycol diacetate Ethylene glycol ethyl ether acetate Ethylene glycol methyl ether acetate Ethyl-3-ethoxypropionate Ethyl hexyl phthalate Ethyl propionate Ethyl propionate Fatty acids (saturated, 14+) Glycerol polyalkoxylate Glyceryl triacetate Glycidyl ester of 10 trialkyl acetic acid Gylcidyl ester of tridecylacetic acid eptyl acetate exyl acetate Lauric acid Lecithin Magnesium long chain alkaryl sulfonate (11 50) Magnesium long chain alkyl phenate sulfide (8 20) Magnesium long chain alkyl salicylate (11+) 3-Methoxybutyl acetate 1-Methoxy-2-propyl acetate Methyl acetate Methyl acetoacetate Methyl amyl acetate Methyl butyrate Methyl formate 3-Methyl-3-methoxybutyl acetate Methyl salicylate Metolachlor Naphthalene sulfonic acid, sodium salt solution (40% or less) Nonyl acetate n-octyl acetate Octyl decyl adipate Oil, edible: Beechnut astor ocoa butter oconut 2 od liver orn otton seed Fish 2 Groundnut azelnut Lard Lanolin Nutmeg butter Olive Palm 2 Palm kernel Peanut Poppy Poppy seed Raisin seed Rapeseed Rice bran Safflower

78 78 Salad Sesame Soya bean Sunflower Sunflower seed Tucum Vegetable Walnut Oil, misc: Animal oconut oil, fatty actid methyl ester otton seed oil, fatty acid Lanolin Palm kernel oil, fatty acid methyl ester Palm oil, methyl ester Pilchard Perilla Soapstock Soyabean (epoxidized) Tall Tall, fatty acid 2 Tung Olefin/Alkyl ester copolymer (molecular weight 2000+) Oleic acid Palm kernel acid oil Palm kernel acid oil, methyl ester Palm stearin n-pentyl propionate Poly(2-8)alkylene glycol monoalkyl(1 6) ether acetate Polydimethylsiloxane Polyferric sulfate solution Polymethylsiloxane Poly(20)oxyethylene sorbitan monooleate Polysiloxane Polyolefin aminoester salt Polyolefin ester (28 250) Polyolefin phosphorosulfide, barium derivative (28 250) Potassium formate solution Potassium oleate Potassium salt of polyolefin acid Propyl acetate Propylene carbonate Propylene glycol methyl ether acetate Sodium acetate, Glycol, Water mixture (not containing Sodium hydroxide) 2 Sodium acetate solution Sodium benzoate solution Sodium dimethyl naphthalene sulfonate solution 2 Sodium long chain alkyl salicylate (13+) Sodium naphthalene sulfonate solution Soyabean oil (epoxidized) Stearic acid Tall oil Tall oil fatty acid ( Resin acids less than 20% ) 2 Tallow 2 Tallow fatty acid 2 Tributyl phosphate Tricresyl phosphate Tridecanoic acid Tridecyl acetate Triethylene glycol dibenzoate Triethylene glycol di-(2- ethylbutyrate) Triethyl phosphate Triethyl phosphite 2 Triisooctyl trimellitate 2 Triisopropylated phenyl phosphates 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate 2,2,4-Trimethyl-1,3-pentanediol-1- isobutyrate 2,2,4-Trimethyl-3-pentanol-1- isobutyrate Trimethyl phosphite 2 Trisodium nitrilotriacetate Trixylyl phosphate Trixylenyl phosphate Vegetable acid oils and distillates, n.o.s. Vegetable oils, n.o.s. Waxes: arnauba Zinc alkaryl dithiophosphate (7 16) Zinc alkyl dithiophosphate (3 14) 35. Vinyl alides Vinyl chloride Vinylidene chloride 36. alogenated ydrocarbons Benzyl chloride Bromochloromethane arbon tetrachloride 2 atoxid feedstock 2 hlorinated paraffins (10-13) hlorinated paraffins (14-17) hlorobenzene hlorodifluoromethane hloroform hlorotoluene Dibromomethane Dibutylphenols 3,4-Dichloro-1-butene Dichlorobenzene Dichlorodifluoromethane 1,1-Dichloroethane 1,6-Dichlorohexane 2,2 -Dichloroisopropyl ether Dichloromethane Dichloropropane Ethyl chloride Ethylene dibromide Ethylene dichloride 2 Methyl bromide Methyl chloride Monochlorodifluoromethane n-propyl chloride Pentachloroethane Perchloroethylene 1,1,2,2-Tetrachloroethane 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,1,1-Trichloroethane 2 1,1,2-Trichloroethane Trichloroethylene 2 1,2,3-Trichloropropane 1,1,2-Trichloro-1,2,2-trifluoroethane 37. Nitriles Acetonitrile Adiponitrile Lactonitrile solution Propionitrile Tallow nitrile 38. arbon Disulfide arbon disulfide Sulfolane 39. Sulfolane 40. Glycol Ethers Alkyl (7-11) phenol poly(4-12)ethoxylate Alkyl (9-15) phenyl propoxylate Diethylene glycol 2 Diethylene glycol butyl ether Diethylene glycol dibutyl ether Diethylene glycol diethyl ether Diethylene glycol ethyl ether Diethylene glycol methyl ether Diethylene glycol n-hexyl ether Diethylene glycol phenyl ether Diethylene glycol propyl ether Dipropylene glycol Dipropylene glycol butyl ether Dipropylene glycol methyl ether Ethoxy triglycol Ethylene glycol hexyl ether Ethylene glycol methyl butyl ether Ethylene glycol monoalkyl ethers Ethylene glycol tert-butyl ether Ethylene glycol butyl ether Ethylene glycol dibutyl ether Ethylene glycol ethyl ether Ethylene glycol isopropyl ether Ethylene glycol methyl ether Ethylene glycol phenyl ether Ethylene glycol phenyl ether, Diethylene glycol phenyl ether mixture Ethylene glycol propyl ether exaethylene glycol Methoxy triglycol Nonyl phenol poly(4+)ethoxylates Pentaethylene glycol methyl ether Polyalkylene glycol butyl ether Polyalkylene glycols, Polyalkylene glycol monoalkyl ethers mixtures Polyethylene glycols Polyethylene glycol dimethyl ether

79 79 Poly(2-8)alkylene glycol monoalkyl(1 6) ether Polyethylene glycol monoalkyl ether Polypropylene glycol methyl ether Polypropylene glycols Poly(tetramethylene ether) glycols (mw ) Polytetramethylene ether glycol n-propoxypropanol Propylene glycol monoalkyl ether Propylene glycol ethyl ether Propylene glycol methyl ether Propylene glycol n-butyl ether Propylene glycol phenyl ether Propylene glycol propyl ether Tetraethylene glycol Tetraethylene glycol methyl ether Triethylene glycol Triethylene glycol butyl ether Triethylene glycol butyl ether mixture Triethylene glycol ether mixture Triethylene glycol ethyl ether Triethylene glycol methyl ether Tripropylene glycol Tripropylene glycol methyl ether 41. Ethers Alkaryl polyether (9 20) tert-amyl methyl ether Butyl ether 2,2 -Dichloroethyl ether Diethyl ether Diglycidyl ether of Bisphenol A Diglycidyl ether of Bisphenol F Dimethyl furan 1,4-Dioxane Diphenyl ether Diphenyl ether, Diphenyl phenyl ether mixture Ethyl tert-butyl ether 2 Ethyl ether Long chain alkaryl polyether (11 20) Methyl-tert-butyl ether 2 Methyl tert-pentyl ether Propyl ether Tetrahydrofuran 1,3, 5-Trioxane Polyether (molecular weight 2000+) 42. Nitrocompounds o-hloronitrobenzene Dinitrotoluene Nitrobenzene Nitroethane Nitroethane, 1-Nitropropane mixture Nitropropane Nitropropane, Nitroethane mixtures Nitrotoluene 43. Miscellaneous Water Solutions Alkyl polyglucoside solutions Aluminum sulfate solution 2 2-Amino-2-hydroxymethyl-1,3- propanediol solution Ammonium bisulfite solution 2 Ammonium lignosulfonate solution Ammonium nitrate, Urea solution (not containing Ammonia) Ammonium polyphosphate solution Ammonium sulfate solution Ammonium thiosulfate solution Sulfonated polyacrylate solutions 2 alcium bromide solution alcium chloride solution alcium lignosulfonate solution aramel solutions lay slurry orn syrup Dextrose solution 2,4-Dichlorophenoxyacetic acid, Diethanolamine salt solution 2,4-Dichlorophenoxyacetic acid, Triisopropanolamine salt solution 2 Diethanolamine salt of 2,4- Dichlorophenoxyacetic acid solution Diethylenetriamine pentaacetic acid, pentasodium salt solution Dodecyl diphenyl ether disulfonate solution Drilling brine (containing alcium, Potassium, or Sodium salts) Drilling brine (containing Zinc salts) Drilling mud (low toxicity) ( if nonflammable or non-combustible ) Ethylenediaminetetracetic acid, tetrasodium salt solution Ethylene-Vinyl acetate copolymer emulsion Ferric hydroxyethylethylenediamine triacetic acid, trisodium salt solution 2 Fish solubles ( water based fish meal extracts ) Fructose solution Fumaric adduct of Rosin, water dispersion examethylenediamine adipate solution N-(ydroxyethyl)ethylene diamine triacetic acid, trisodium salt solution Kaolin clay slurry Latex, liquid synthetic Lignin liquor Liquid Streptomyces solubles l-lysine solution N-Methylglucamine solution Naphthenic acid, sodium salt solution Potassium chloride solution Potassium thiosulfate solution Rosin soap (disproportionated) solution Sewage sludge, treated Sodium alkyl sulfonate solution Sodium hydrogen sulfite solution Sodium lignosulfonate solution Sodium polyacrylate solution 2 Sodium salt of Ferric hydroxyethylethylenediamine triacetic acid solution Sodium silicate solution 2 Sodium sulfide solution Sodium sulfite solution Sodium tartrates, Sodium succinates solution Sulfonated polyacrylate solutions 2 Tall oil soap (disproportionated) solution Tetrasodium salt of EDTA solution Titanium dioxide slurry Triisopropanolamine salt of 2,4- Dichlorophenoxyacetic acid solution Urea, Ammonium nitrate solution (not containing Ammonia) Urea, Ammonium phosphate solution Urea solution Vegetable protein solution (hydrolysed) Water Footnotes to Table II 1 Because of very high reactivity or unusual conditions of carriage or potential compatibility problems, this product is not assigned to a specific group in the ompatibility hart. For additional compatibility information, contact ommandant (G-ENG-5), Attn: azardous Materials Division, U.S. oast Guard Stop 7509, 2703 Martin Luther King Jr. Avenue SE., Washington, D Telephone or hazmatstandards@uscg.mil. 2 See Appendix I Exceptions to the hart

80 80 Appendix I to Part 150 Exceptions to the hart (a). The binary combinations listed below have been tested as prescribed in Appendix III and found not to be dangerously reactive. These combinations are exceptions to the ompatibility hart (Figure 1) and may be stowed in adjacent tanks. Member of reactive group ompatible with Acetone (18) Diethylenetriamine (7) Acetone cyanohydrin (0) Acetic acid (4) Acrylonitrile (15) Triethanolamine (8) 1,3-Butylene glycol (20) Morpholine (7) 1,4-Butylene glycol (20) Ethylamine (7) Triethanolamine (8) gamma-butyrolactone (0) N-Methyl-2-pyrrolidone (9) austic potash, 50% or less (5) Isobutyl alcohol (20) Ethyl alcohol (20) Ethylene glycol (20) Isopropyl alcohol (20) Methyl alcohol (20) iso-octyl alcohol (20) austic soda, 50% or less (5) Butyl alcohol (20) tert-butyl alcohol, Methanol mixtures Decyl alcohol (20) iso-decyl alcohol (20) Diacetone alcohol (20) Diethylene glycol (40) Dodecyl alcohol (20) Ethyl alcohol (20) Ethyl alcohol (40%, whiskey) (20) Ethylene glycol (20) Ethylene glycol, Diethylene glycol mixture (20) Ethyl hexanol (Octyl alcohol) (20) Methyl alcohol (20) Nonyl alcohol (20) iso-nonyl alcohol (20) Propyl alcohol (20) iso-propyl alcohol (20) Propylene glycol (20) Sodium chlorate solution (0) iso-tridecanol (20) tert-dodecanethiol (0) Acrylonitrile (15) Diisodecyl phthalate (34) Methyl ethyl ketone (18) iso-nonyl alcohol (20) Perchloroethylene (36) iso-propyl alcohol (20) Tall oil, crude Dodecyl and Tetradecylamine Tall oil, fatty acid (34) mixture (7) Ethylenediamine (7) Butyl alcohol (20) tert-butyl alcohol (20) Butylene glycol (20) reosote (21) Diethylene glycol (40) Ethyl alcohol (20) Ethylene glycol (20) Ethyl hexanol (20) Glycerine (20) Isononyl alcohol (20) Isophorone (18) Methyl butyl ketone (18) Methyl iso-butyl ketone (18) Methyl ethyl ketone (18) Member of reactive group ompatible with Propyl alcohol (20) Propylene glycol (20) Oleum (0) exane (31) Dichloromethane (36) Perchloroethylene (36) 1,2-Propylene glycol (20) Diethylenetriamine (7) Polyethylene polyamines (7) Triethylenetetramine (7) Sodium dichromate, 70% (0) Methyl alcohol (20) Sodium hydrosulfide solution (5) Methyl alcohol (20) Iso-Propyl alcohol (20) Sulfuric acid (2) oconut oil (34) oconut oil acid (34) Palm oil (34) Tallow (34) Sulfuric acid, 98% or less (2) hoice white grease tallow (34) (b). The binary combinations listed below have been determined to be dangerously reactive, based on either data obtained in the literature or on laboratory testing which has been carried out in accordance with procedures prescribed in Appendix III. These combinations are exceptions to the ompatibility hart (Figure 1) and may not be stowed in adjacent tanks. Acetone cyanohydrin (0) is not compatible with Groups 1-12, 16, 17 and 22. Acrolein (19) is not compatible with Group 1, Non-Oxidizing Mineral Acids. Acrylic acid (4) is not compatible with Group 9, Aromatic Amines. Acrylonitrile (15) is not compatible with Group 5 (austics). Alkylbenzenesulfonic acid (0) is not compatible with Groups 1-3, 5-9, 15, 16, 18, 19, 30, 34, 37, and strong oxidizers. Allyl alcohol (15) is not compatible with Group 12, Isocyanates. Alkyl(7-9) nitrates (34) is not compatible with Group 1, Nonoxidizing Mineral Acids. Aluminum sulfate solution (43) is not compatible with Groups Ammonium bisulfite solution (43) is not compatible with Groups 1, 3, 4, and 5. Benzenesulfonyl chloride (0) is not compatible with Groups 5-7, and 43. 1,4-Butylene glycol (20) is not compatible with austic soda solution, 50% or less (5). gamma-butyrolactone (0) is not compatible with Groups Resinfeed (DSM) (32) is not compatible with Group 2, Sulfuric acid. arbon tetrachloride (36) is not compatible with Tetraethylenepentamine or Triethylenetetramine, both Group 7, Aliphatic amines. atoxid feedstock (36) is not compatible with Group 1, 2, 3, 4, 5, or 12. austic soda solution, 50% or less (5) is not compatible with 1,4- Butylene glycol (20). 1-(4-hlorophenyl)-4,4-dimethyl pentan-3-one (18) is not compatible with Group 5 (austics) or 10 (Amides). rotonaldehyde (19) is not compatible with Group 1, Non-Oxidizing Mineral Acids. yclohexanone, yclohexanol mixture (18) is not compatible with Group 12, Isocyanates. 2,4-Dichlorophenoxyacetic acid, Triisopropanolamine salt solution (43) is not compatible with Group 3, Nitric Acid. 2,4-Dichlorophenoxyacetic acid, Dimethylamine salt solution (0) is not compatible with Groups 1-5, 11, 12, and 16.

81 81 Diethylenetriamine (7) is not compatible with 1,2,3- Trichloropropane, Group 36, alogenated hydrocarbons. Dimethyl hydrogen phosphite (34) is not compatible with Groups 1 and 4. Dimethyl naphthalene sulfonic acid, sodium salt solution (34) is not compatible with Group 12, Formaldehyde, and strong oxidizing agents. Dodecylbenzenesulfonic acid (0) is not compatible with oxidizing agents and Groups 1, 2, 3, 5, 6, 7, 8, 9, 15, 16, 18, 19, 30, 34, and 37. Ethylenediamine (7) and Ethyleneamine EA 1302 (7) are not compatible with either Ethylene dichloride (36) or 1,2,3- Trichloropropane (36). Ethylene dichloride (36) is not compatible with Ethylenediamine (7) or Ethyleneamine EA 1302 (7). Ethylidene norbornene (30) is not compatible with Groups 1-3 and Ethyl-3-propylacrolein (19) is not compatible with Group 1, Non- Oxidizing Mineral Acids. Ethyl tert-butyl ether (41) is not compatible with Group 1, Nonoxidizing mineral acids. Ferric hydroxyethylethylenediamine triacetic acid, Sodium salt solution (43) is not compatible with Group 3, Nitric acid. Fish oil (34) is not compatible with Sulfuric acid (2). Formaldehyde (over 50%) in Methyl alcohol (over 30%) (19) is not compatible with Group 12, Isocyanates. Formic acid (4) is not compatible with Furfural alcohol (20). Furfuryl alcohol (20) is not compatible with Group 1, Non-Oxidizing Mineral Acids and Formic acid (4). 2-ydroxyethyl acrylate (14) is not compatible with Group 5, 6, or 12. Isophorone (18) is not compatible with Group 8, Alkanolamines. Magnesium chloride solution (0) is not compatible with Groups 2, 3, 5, 6 and 12. Mesityl oxide (18) is not compatible with Group 8, Alkanolamines. Methacrylonitrile (15) is not compatible with Group 5 (austics). Methyl tert-butyl ether (41) is not compatible with Group 1, Nonoxidizing Mineral Acids. NIAX POLYOL APP 240 (0) is not compatible with Group 2, 3, 5, 7, or 12. o-nitrophenol (0) is not compatible with Groups 2, 3, and Octyl nitrates (all isomers), see Alkyl(7-9) nitrates. Oleum (0) is not compatible with Sulfuric acid (2) and 1,1,1- Trichloroethane (36). Phthalate based polyester polyol (0) is not compatible with group 2, 3, 5, 7 and 12. Polyglycerine, Sodium salts solution (20) is not compatible with Groups 1, 4, 11, 16, 17, 19, 21 and 22. Propylene, Propane, MAPP gas mixture (containing 12% or less MAPP gas) (30) is not compatible with Group 1 (Non-oxidizing mineral acids), Group 36 (alogenated hydrocarbons), nitrogen dioxide, oxidizing materials, or molten sulfur. Sodium acetate, Glycol, Water mixture (1% or less Sodium hydroxide) (34) is not compatible with Group 12 (Isocyanates). Sodium chlorate solution (50% or less) (0) is not compatible with Groups 1-3, 5, 7, 8, 10, 12, 13, 17 and 20. Sodium dichromate solution (70% or less) (0) is not compatible with Groups 1-3, 5, 7, 8, 10, 12, 13, 17 and 20. Sodium dimethyl naphthalene sulfonate solution (34) is not compatible with Group 12, Formaldehyde and strong oxidizing agents. Sodium hydrogen sulfide, Sodium carbonate solution (0) is not compatible with Groups 6 (Ammonia) and 7 (Aliphatic amines). Sodium hydrosulfide (5) is not compatible with Groups 6 (Ammonia) and 7 (Aliphatic amines). Sodium hydrosulfide, Ammonium sulfide solution (5) is not compatible with Groups 6 (Ammonia) and 7 (Aliphatic amines). Sodium polyacrylate solution (43) is not compatible with Group 3, Nitric Acid. Sodium silicate solution (43) is not compatible with Group 3, Nitric Acid. Sodium sulfide, hydrosulfide solution (0) is not compatible with Groups 6 (Ammonia) and 7 (Aliphatic amines). Sodium thiocyanate (56% or less) (0) is not compatible with Groups 1-4. Sulfonated polyacrylate solution (43) is not compatible with Group 5 (austics). Sulfuric acid (2) is not compatible with Fish oil (34), or Oleum (0). Tall oil fatty acid ( Resin acids less than 20% ) (34) is not compatible with Group 5, austics. Tallow fatty acid (34) is not compatible with Group 5, austics. Tetraethylenepentamine (7) is not compatible with arbon tetrachloride, Group 36, alogenated hydrocarbons. 1,2,3-Trichloropropane (36) is not compatible with Diethylenetriamine, Ethylenediamine, Ethyleaneamine EA 1302, or Triethylenetetramine, all Group 7, Aliphatic amines. 1,1,1-Trichloroethane (36) is not compatible with Oleum (0). Trichloroethylene (36) is not compatible with Group 5, austics. Triethylenetetramine (7) is not compatible with arbon tetrachloride, or 1,2,3-Trichloropropane, both Group 36, alogenated hydrocarbons. Triethyl phosphite (34) is not compatible with Groups 1, and 4. Trimethyl phosphite (34) is not compatible with Groups 1 and 4. 1,3,5-Trioxane (41) is not compatible with Group 1 (non-oxidizing mineral acids) and Group 4 (Organic acids). Appendix II to Part 150 Explanation of Figure 1 Definition of a hazardous reaction As a first approximation, a mixture of two cargoes is considered hazardous when, under specified condition, the temperature rise of the mixture exceeds 25 or a gas is evolved. It is possible for the reaction of two cargoes to produce a product that is significantly more flammable or toxic than the original cargoes even though the reaction is non-hazardous from temperature or pressure considerations, although no examples of such a reaction are known at this time. hart format There are different degrees of reactivity among the various cargoes. Many of them are relatively non-reactive: For example, aromatic hydrocarbons or paraffins. Others will form hazardous combinations with many groups: For example, the inorganic acids. The cargo groups in the compatibility chart are separated into two categories: 1 through 22 are Reactive Groups and 30 through 43 are argo Groups. Left unassigned and available for future expansion are groups 23 through 29 and those past 43. Reactive Groups contain products which are chemically the most reactive; dangerous combinations may result between members of different Reactive Groups and between members of Reactive Groups and argo Groups. Products assigned to argo Groups, however, are much less reactive; dangerous combinations involving these can be formed only with members of certain Reactive Groups. argo Groups do not react hazardously with one another. Using the ompatibility hart The following procedure explains how the compatibility chart should be used to find compatibility information: (1) Determine the group numbers of the two cargoes by referring to the alphabetical listing of cargoes and the corresponding groups (Table I). Many cargoes are listed under their parent names; unless otherwise indicated, isomers or mixtures of isomers of a particular cargo are assigned to the same group. For example, to find the group number for Isobutyl Alcohol, look under the parent name Butyl Alcohol. Similarly, the group number for para-xylene is found under

82 82 the entry Xylene. If a cargo cannot be found in this listing, contact the oast Guard for a group determination (see ). (2) If both group numbers are between 30 and 43 inclusive, the products are compatible and the chart need not be used. (3) If both group numbers do not fall between 30 and 43 inclusive, locate one of the numbers on the left of the chart (argo Groups) and the other across the top (Reactive Groups). (Note that if a group number is between 30 and 43, it can only be found on the left side of the chart.) The box formed by the intersection of the column and row containing the two numbers will contain one of the following: (a) Blank The two cargoes are compatible. (b) X The two cargoes are not compatible. (Note that reactivity may vary among the group members. Refer to Table I or Table II to find whether the products in question are referenced by a footnote which indicates that exceptions exist and are listed in Appendix I. Unless the combination is specifically mentioned in Appendix I, it is compatible.) [GD 75 59, 45 FR 70263, Oct. 23, 1980, as amended by GD , 50 FR 33046, Aug. 16, 1985] Examples ombination Groups ompatible Butyraldehyde/Acetic Acid 19/4 Yes. Allyl Alcohol/Toluene Diisocyanate 15/12 No. Decene/Ethyl Benzene 30/32 Yes. Ethanolamine/Acetone 8/18 Yes. Ammonia/Dimethylformamide 6/10 No. Appendix III to Part 150 Testing Procedures for Determining Exceptions to the hart experimental procedure for evaluating binary chemical reactivity General safety precautions hemical reactivity tests have, by their nature, serious potential for injuring the experimenter or destroying equipment. The experimenter should 1) have knowledge of the magnitude of the reactivity to be expected, 2) use adequate facilities and protective equipment to prevent injury from splatter of materials or release of fumes, and 3) start on a small scale so that unexpected reactions can be safely contained. All tests should be performed in a well-ventilated laboratory hood provided with shields. Testing chemicals other than liquids The procedure outlined below was developed for chemicals which are liquids at ambient temperatures. If one or both chemicals are normally shipped at elevated temperatures, the same procedure may be followed except the chemicals are tested at their respective shipping temperatures and the oil bath in Step 3 is maintained at a level 25 above the higher temperature. This information is then indicated on the data sheet. If one of the chemicals is a gas at ambient temperatures, consult the oast Guard for additional instructions before proceeding with the compatibility test. Step 1 Objective To determine if the test chemicals react violently and present a safety hazard in further tests. Procedure Place 0.5ml of one (A) of the test chemicals in a mm test tube. lamp the test tube to a stand behind a safety shield (in a hood). arefully add from a dropper 0.5ml of the other substance (B). Shake to induce mixing. If no immediate reaction occurs, retain the mixture for at least 10 minutes to check for a delayed reaction. Results If a violent reaction occurs, such as sputtering, boiling of reactants or release of fumes, record the results on the Data Sheet (appendix IV) and do not proceed to Step 2. If no reaction or a minor reaction occurs, proceed to Step 2. Step 2 Objective To determine the heat of reaction of two chemicals on mixing under specified conditions. Procedure These separate mixes of the proposed binary combination will be tested. These are 2 ml : 18 ml, 10 ml : 10 ml, and 18 ml : 2 ml, respectively, to result in a final mixture of about 20 ml in each case. A reference-junctioned thermocouple is prepared by inserting two lengths of 20 gauge or finer iron-constantan or chromelalumel duplex thermocouple wire into glass capilary sheaths. The common wire of each probe is joined, while the other wire of each is connected to a strip-chart recorder. The thermocouple probe which produces a negative pen deflection upon warming is the reference junction and is placed in a test tube of water at ambient laboratory temperature. The other probe is placed near the bottom of a Dewar flask of about 300ml capacity, such that the thermocouple will be below the surface of the test mixture. The Dewar flask is equipped with a magnetic stirrer having a stirring bar coated with an inert material such as a flourinated hydrocarbon. Start the temperature recorder and stirrer. Deliver the test chemicals to the Dewar Flask simultaneously from separate graduated syringes. If an exothermic reaction occurs, continue the test until the maximum temperature is reached and begins to subside. If no apparent reaction occurs, continue the test for at least 30 minutes to check for a delayed reaction. Stop agitation and observe the mixture at five-minute intervals to determine if the mixture is miscible, if gases are evolved, or if other visible changes occur. In the interest of safety, a mirror can be used for these observations. Repeat the above test for the other mixture combinations. Results Record the results in the appropriate places on the Data Sheet. If no reaction occurs or if the temperature rise is less than 25, proceed to Step 3. If the observed temperature rise exceeds 25 or gases are evolved, do not proceed to Step 3. Step 3 Objective To determine if exothermic reactions occur at temperatures up to 50. Procedure If a non-hazardous reaction occurred in Step 2, the ratio of chemicals which resulted in the greatest temperature rise will be tested. Fresh chemicals will be used with a total volume for this test of about 10ml (a ratio of 1ml:9ml, 5ml:5ml, or 9ml:1ml). If no reaction was observed in Step 2, use a ratio of 5ml:5ml. Using the thermocouple prepared for Step 2, insert the reference probe into a mm test tube containing 10ml of water. Place the other probe into an empty test tube. Start the temperature recorder and add the two chemicals of the combination, one at a time, to the empty test tube. Lower the two test tubes into an oil bath maintained at 50 ±2. old the samples in the oil bath until the maximum temperature differential is recorded, and in all cases at least 15 minutes. Observe the test mixture to determine if gases are evolved or if other visible changes occur. Follow prescribed safety precautions. Results Record the maximum differential temperature measured, the time required to reach this temperature, and any other observations in the proper space on the Data Sheet. Send a copy of the Data Sheet for each binary chemical mixture tested to: ommandant (G-MSO), U.S. oast Guard, Washington, D

83 83 Tank oating and Tank onstruction Materials Most tanks in modern tankers are coated. i.e. covered by a protective layer of a substance mostly of a polymer nature. A number of coatings with very specific properties has been developed for use in chemical tankers, and to avoid damage to the coating it is necessary to have a thorough knowledge of their possibilities and to treat them properly. Tanks are coated for the following purposes. 1. Diminishing of corrosion in the tanks. 2. Avoidance of contamination of the cargo by ferrous substances such as rust or by residues from former cargoes. 3. Easier tank cleaning and gas freeing. 4. Easier tank inspection To comply with the various demands which are aroused for chemical tankers several types of coatings have been developed in all kinds of qualities. Some of the more important are: Epoxy: Polyurethane: Neoprene: Zinksilicate: MarineLINE Resistance list Resistant to many chemicals and light organic acids, poor resistance to strong solvents such as ketones. omparable to epoxy but with better resistance to fatty acids, and poorer resistance to alkalines. Primarily for acids and alkalines. Poorer resistance to solvents and hydrocarbons. Very resistant to solvents and hydrocarbons, but normally only resistant to products in the p-range from 6.5 to 9. MarineLINE is a multifunctional polymer coating with a very dense, highly cross-linked molecular structure. The resistance is very good and also the physical properties are promising. This kind of coating has been on the market since mid 1990-ies. Prior to any loading in a vessel with coated tanks the Resistance Lists of the coating should be consulted to find any restrictions valid for the product. If a product is not included in the list or if in doubt, the company should be contacted to get instructions. Any errors in this field might lead to ruined coating and cargo. On next two pages is shown an example on a resistance list from the paint manufacturer empel. empel s cargo tank protection comprises three different makes of coating i.e. a zinc silicate based coating and two qualities of an epoxy coating. The resistant list can be accessed from empel s argo protection Guide is a web-based database to search for electronic information on the chemical resistance of

84 84 empel s tank linings towards a large number of chemicals/ cargoes Information in the argo Protection Guide can be found for the following tank linings: EMPEL s GALVOSIL (zinc ethyl silicate) EMPADUR (phenolic epoxy) EMPADUR (amine epoxy) The resistance list offers a lot of information, for example: -hemical formula, if known. The name of the product. UN number, if any MARPOL pollution category Ship Type requirement Resistance information and limitations Methyl Acrylate carried in a cargo tank coated with EMPADUR is used as an example: Marstal Navigationsskole April 14

85 85 A thorough explanation of the different comments is given in the introduction to the list, but below is as an example shown Note 13: Repairs of the coating should only be undertaken in accordance with instructions from the manufacturer of the coating. Normally the ompany should be consulted before undertaking such repairs due to the possibility of infringement of warranty etc. The use of hot water during tank cleaning should also be considered well as most coatings have a temperature limit of approximately 70. If packing or heating-coils of special materials are incorporated in the cargo system, the resistance of those should also be considered. Marstal Navigationsskole April 14

86 86 Stainless steel Vessels with stainless steel tanks are considered to be resistant to most products, but anyway care should be exercised as some products will damage the surface of the steel. The most problematic products in this respect are of course the strong inorganic acids such as Sulphuric Acid and Phosphoric Acid. Any tank cleaning involving sea water should always be followed by a fresh water wash in order to remove traces of hloride as sea water and chloride is very corrosive to stainless steel. Below is shown an exempt of a resistance list for a high grade stainless steel. Remarks to Resistance : -o- Marstal Navigationsskole April 14

87 87 Passivation If the tank surface has been damaged it might be necessary to perform a new passivation of the stainless steel surface. The passivation can be performed in several ways, but the most general is to spray the tank with a 20% nitric acid solution. In all cases it is always a good idea to consult the manufacturer of the steel plates before a passivation is carried out. Advantages and disadvantages of zink silicate and epoxy paint Zinc silicate Over the years inorganic zinc-rich coatings have proved themselves to be durable tanklinings in a variety of service applications. The paint itself consists of a single layer, typically of 100 micron thickness, comprising of inorganic silicates (or ethyl silicate) pigmented with a high percentage of elemental zinc powder. Usually the elemental zinc content is greater than 90 per cent of the paint film by weight. omplex curing reactions bind the zinc particles in an inorganic silicate matrix which chemically adheres the coating to the steel substrate. The result is a paint system with outstanding mechanical strength. The paint film is porous in nature, in that the cargo can physically penetrate into the interstictices formed between the zinc particles and the complex silicate matrix binder. The porosity of these paint systems has two consequences. On the good side, very volatile solvent-like cargoes can be rapidly and virtually completely removed from the coating by evaporation/ventilation upon completion of discharge. Thus the potential risk of contamination of the subsequent cargo is virtually nonexistent as no residues remain behind within the coating. On the other hand, the same cannot be said for heavier oil-like (residual) cargoes (e.g. lube oils), which cannot be removed by evaporation/ventilation. The presence of these substances within the pores of the coating presents the vessel s crew with tank cleaning problem and the risk of contamination of the next cargo is considerably increased especially if the next cargo is a good solvent (e.g. motor gasoline or benzene, etc.). In general the life expectancy of these coatings is proportional to their thickness. This is because corrosion protection is afforded to the steel substrate by virtue of a sacrificial cathodic mechanism whereby the zinc content of the coating ultimately becomes depleted. A major disadvantage of zinc silicate coatings of this type is their inability to resist cargoes in anything other than narrow neutral range of acidity/alkalinity. Thus strong acids and alkalies, vegetable oils and solvents prone to hydrolysis (reaction with water to produce acids) cannot Marstal Navigationsskole April 14

88 88 be carried in cargo tanks lined with this type of paint. For many shipowners this places an unacceptable restraint on their trading activities and for this reason they elect to have some or all of the cargo tanks of their vessel coated with organic paint systems. Epoxy paint Absorption/desorption of cargo Organic epoxy paint coatings comprise of a family of products having slightly different properties. Suffice it to say that epoxy paints consist of an organic resin system which, when mixed with a hardener, forms a coating film that produces a three-dimensional cross-linked array of chemical bonds between the resin molecules. When fully cured, this film offers corrosion protection to the steel substrate by virtue forming a barrier between the cargo and the steel. The differing epoxy types, e.g. pure epoxy, phenolic epoxy, isocyanate epoxy, etc., form cross-linkages to different degrees resulting in increased resistance to greater range of cargoes as the extent of cross-linking increases. Typically, organic coatings are applied in several layers (three coats each of approximately 100 micron thickness) to a steel substrate pre-prepared to a high standard using blasting techniques. Temperature and humidity control of tank atmospheres are usually necessary during application of the coating as is attention to post-cure conditions. In contrast to inorganic zinc paints, epoxy systems are resistant to strong acids and alkalies and do not, in general, absorb significant quantities of oil-like (residual) substances. Such substances merely stay on the surface of the paint where they can be removed by conventional cleaning methods. Organic coatings do, however, absorb significant quantities of solvent-like cargoes into the paint film and subsequently desorb (release) these solvent residues following discharge of the cargo. It is this property of absorption and desorption of cargo residues to and from organic coatings that has resulted in numerous cargo contamination incidents. Generally, absorption of a substance into a paint film proceeds at an initially rapid (linear) rate and then falls to zero when the film becomes saturated. In an analogous way, desorption is initially rapid and eventually tails-off to a level that does not necessarily represent a situation where all of the absorbed substance is removed from the paint film but a state, nonetheless, where no more is desorbed. This is shown diagrammatically in the figure below. (The diagram is notional only to illustrate the underlying principles and are not meant for reference). Marstal Navigationsskole April 14

89 Weight of Absorbed argo (g/m2) 89 Absorption/Desorption of a argo in an Organic Tanklining Days It can be seen that in the above example the quantity of absorbed cargo rapidly reaches a maximum within three days but thereafter stays approximately at that level for the duration of the laden passage. Following discharge (day 14) desorption occurs at a rapid rate until after four days there is no significant further loss of the retained species. It is emphasised that different epoxy types absorb and desabsorb to differing extents and indeed considerable variation is known to exist between similar generic types of epoxy paint produced by the various paint manufacturers. In general it can be said that cargoes having small molecular structures are able to penetrate organic coatings to a greater extent than those cargoes with larger molecules, thus methanol is known to be a very penetrative cargo and is widely acknowledged within the industry as being one of the most aggressive cargoes that can be carried in organic coated tanks. Absorption/desorption characteristics for each cargo will differ. The rate of absorption and desorption is critically influenced not only by thickness of the paint film but also by temperature. Absorption and desorption rates are increased as temperature is raised. Thus it is in the owners interests to carry cargo at the lowest practical temperature (to lessen absorption) and to increase the air/steel temperature of their cargo tanks following completion of discharge of any cargo in order to maximise the rate of desorption. It is also known that water greatly influences the rate of absorption/desorption, some paint Marstal Navigationsskole April 14

90 90 systems having a considerably lower rate of sorption when saturated with water. This effect has a direct bearing on the type of tank cleaning which should be carried out after discharge. It can be appreciated that certain cargoes cannot be entirely eradicated from some paint systems in a reasonable time between discharge of one cargo and the lifting of the next. These retained residues subsequently contaminate the next cargo by the mechanism of continued desorption and can sometimes be found to contaminate second, third and even later subsequent cargoes. This is especially true for highly odiforous cargoes such as acrylates and styrene monomer where even sub-ppm contaminations can, in the first instance, be readily detected by simple odour evaluation tests. In an incident, styrene monomer has been shown to be the contaminant in a vegetable oil cargo despite being the third last cargo. Whilst the concentration of styrene monomer was not great ( ppm wt) modern instrumental analytical techniques are more than capable of detecting such trace concentrations and such detection is sufficient to give rise to a claim. Vegetable oil cargoes are especially susceptible to contamination due to the fact that they are often carried at elevated temperatures, which considerably increase the rate of desorbing contaminants. Reducing the risk of contamination incidents Faced with a conflicting interest between trading economics and the possibility of contamination of the cargo, what can a prudent owner do to reduce the risk of contamination incidents? - oating choice is crucial. The absorption/desorption characteristics of the paint systems currently available to owners differ significantly. Some paints (the best) absorb lesser quantities of cargo than similar specified products from rival paint companies and desorb more completely. Selection of such coating systems significantly reduces the risk of contamination. In future, paint manufacturers will formulate coatings that will outperform even the best of those available today. Allow coatings to desorb for as long as possible. The rate of desorption is greatly increased by raising the temperature of the coating within the tank. It is not necessary to continuously ventilate the tank, this has been shown to be ineffective. Avoid the stowage of sensitive cargoes such as refined foodstuffs, potable ethanol, methanol, ethylene glycol, isopropanol, etc. in tanks where incompatible cargoes have been stowed as first, second and, if possible, third/fourth last. Marstal Navigationsskole April 14

91 91 If unfavourable stowage is unavoidable, charterers should be fully advised of the contamination potential and an indemnity sought. As a general rule, paint systems for tanks should not develop substances that may contaminate the cargo. This is particularly important for cargoes intended for human consumption and pure chemical cargoes. Paint systems for tanks for edible and potable cargoes must not develop toxic substances or substances affecting colour or taste. For this reason they need to be officially approved. onsequently, the coating system should not only be resistant to the separate cargoes but also to the alternating action of different cargoes and cargo cleaning procedures. While two successive cargoes may be individually compatible with a tank coating system, a mixture of the two, due to residues of the first cargo, may cause damage. For instance when a cargo containing water follows a Vinyl Acetate Monomer cargo, residues of Vinyl Acetate Monomer in the tank lining (coating) will hydrolyse. By this process Acetic Acid is formed which will cause corrosion and attack the coating. Ethylene Dichloride (ED) and water will form ydrochloric Acid, and hloroform and water form Formic Acid. Therefore, special attention must be paid to additional notes, containing warnings/restrictions, for instance concerning acidity/alkalinity, presence of water in the tanks, cleaning chemicals, cargo residues, etc. Aggressive products and byproducts A zinc silicate rich coating is not resistant to strong acids or alkaline. Its suitability is limited to products in the p range between 5 and 9. The use of acidic or alkaline tank cleaning products must also be avoided. Slight zinc pickup by the cargo is possible, depending on the cargo in question. As mentioned above, certain products, such as esters (acetates, phthalates etc.) and chlorinated or brominated materials can react with water to form acidic compounds. Thus, although these products are suitable for storage in coated tanks when dry, pre presence of water may make them aggressive or totally unacceptable. Such products must therefore be dry and carried in completely dry tanks and water leaks must be avoided. Water contents should not exceed 0.01%, same as 100 ppm. These products may cause some discolouration of the coating. Subsequently cleaning of the tanks may be difficult so that contamination of susceptible cargoes could occur. These products are variable in composition, depending on source, and consequently the effects on the coating can also differ. Marstal Navigationsskole April 14

92 92 are of the coating All personnel, who enter the tank during inspection, control, repair, maintenance etc., must wear soft soled shoes, and this is of special importance for epoxy coated tanks, which have been exposed to chemicals, softening the coating. Tank cleaning chemicals, especially acidic, alkaline and those with strong solvents, may lead to chemical damage of the tank coating if used improperly. A list of accepted tank cleaning chemicals should be available on board, most delivered with the coating resistant list. Vegetable and animal oils, fats, grease and waxes are esters of polyols and fatty acids, and containing mostly free fatty acids as well. If in contact with water at higher temperatures these esters can saponify resulting in increased free fatty acid content. These free fatty acids, especially the short chain types, can be very aggressive to tank coatings. Thus during loading, storage and discharge the acid values should not exceed the maximum values given in the coating resistance list. The fatty acids accepted can be transported only if they are of normal composition and do not contain more than 2% short chain organic acids (below 6). These aggressive cargoes can only be carried when the coating is fully cured. Full cure will for example be obtained after transport of a hot cargo such as lubricating oil, animal oil or vegetable oil at temperatures of 60 for five days. Marstal Navigationsskole April 14

93 93 Safety regulations and precautions in port Loading and discharging Preparation of loading Pre-arrival planning When dangerous chemicals are transported by ship the routines known from traditional oil transport are not sufficient. When loading orders are recieved and when working out information sheets it should be considered if special precautions should be taken, and whether personnel on deck and in the engine-room should have special instructions. When loading orders are received the following should be checked: Are the products mentioned on the ship's "ertificate of Fitness" (of) or in chapter 18 of the IBcode or are they oils as defined in Marpol's Annex I. Are there any restrictions in the IB-code regarding ship type or tank type (this will also be stated in the of) Are there any coating restrictions. Are there any restrictions regarding filling of the tanks because of high densities. Afterwards the cargo can be "laid out" considering trim, heating, and - of course - volumes. In this connection also the filling limits should be taken into account. IB hapter states that tanks carrying liquids at ambient temperatures should be so loaded as to avoid the tank becoming liquid full during the voyage, having due regard to the highest temperature which the cargo may reach. It is normally assumed that a tank may be filled up to 98 % but in order to be quite accurate one may use the formula, which was given in the previous edition of Tanker Safety Guide (hemicals): Filling ratio (% full) = 100 (1 - α ΔT) - S where (α) = coefficient of cubic expansion per. (ΔT) = expected maximum temperature rise ( ). S = Safety margin, usually 2 % of tank vol. During the loading operation all tanks should be stopped before the highest high-level alarm is reached, thus preventing an overflow due to a leaking valve. If necesssary Marstal Navigationsskole April 14

94 94 Important checks after arrival the tanks can then be topped off to a higher level at the end of the loading operation. It should always be considered in which order the tanks have to be filled, and which cargo pipes and valves to be used for each product. Any irregularities should be discussed with the owners as soon as possible to enable the shore organisation to solve eventual problems before arrival. Ship/Shore Safety heck List Prior to commencement of loading the ship will be presented with a Safety heck List. These lists often vary from port to port but the main content is of cause the same. According to IMO such a check should be available in writing and shall comprise safety regulations, handling procedures and emergency procedures. A standard layout can be found i several IMO and IS publications - for example in the "Tanker Safety Guide". The check list is meant to cover all types of tankers and begins with a general part, and then comes different parts covering special types of tankers. In the following is shown the general part and the special part for chemical tankers. In many ports the ship will be presented with additional heck Lists which must be read thoroughly. On the pages are shown the parts of the Ship/Shore Safety heck List that are relevant for a chemical tanker. Marstal Navigationsskole April 14

95 95 Loading Open device (O): Restricted device (R): losed device (): Indirect device (I): Before loading it is very important to check the function of the P/V-valves and the high-level alarms. Loading of chemicals should always start with a slow loading rate in order to assure that the uplining is correct and check for leakage in the cargo piping in use. The maximum loading rate is agreed with the loading master taking note of the construction of the cargo piping, the ship's construction and the danger of the chemical to be loaded. Topping off should be carried out in accordance to the method of gauging stated in the IMO-code, and always recognizing the character of the cargo. Gauging should be carried out in accordance with the specification in chapter 17 column j of the code. The following gauging methods are considered: Gauging with ullage-tape or -stick is allowed through open hatch or ullage port. It is allowed to use a gauging system, which permits minor amount of vapour to come into contact with atmospheric air during the gauging, but in the rest of the time is completely closed. A typical example of such a device is a vertical pipe with a ball valve on top. It is then possible to attach a special instrument to the ball valve,-open the valve and make the gauging. It is allowed to use a system, which penetrates the top of the tank, but moreover is vapour- and liquid tight. Examples are float systems, electronic- or magnetic systems or tank radar. This system does not permit penetration of the tank, so the only way to measure the content of the tank is to weigh the cargo (draft survey), use flow meter or similar. The gas venting system requires special attention when loading chemicals. IMO distinguishes in the product list between open and controlled vent systems and for quite special products systems with safety relief valve. The open tank vent is only allowed for products with flash point above 60 and which does not have any health risk. In all other instances special rules should be adhered to, where an important point is that the gas outlet should be placed at least 6 m above deck and walkway or 3 m above if the ship is fitted with high velocity valves. It is important to notice, when transporting health risky products, if there are special requirements concerning handling of the vapour mentioned in column o in the IMOcode. For many products it is required that the vapour is returned ashore via a so-called vapour-return line.

96 96 If the ship has only one common gas vent system the ship is not able to load different chemicals, which react with each other. For such chemicals it is required that the vapours are effectively separated. When loading air-reactive chemicals some special provisions have to be taken. It might be necessary to use inert gas produced on board, use nitrogen bought ashore or produced on board. For chemicals that react slowly with air it may be sufficient to use padding i.e. changing of tank atmosphere after end of loading. The technique and the problems in regard to these things is dealt with in the special chapter on inert gas etc. Information about which products that require inerting can be found in the IMO-code and handbooks, but of cause it is also very important to follow the instructions in the charter party. Ullaging and sampling require special attention when loading dangerous chemicals. It is wise to allow some time for the products to settle down before taking the final ullage. IS recommends not to take samples or ullages until 30 minutes after ending of loading. Beware of overpressure in the tank when opening ullage ports etc. Sampling which is extremely important in the chemical trade should be taken with care. Where it is possible the samples should be taken at test cocks or by using the closed sampling system if fitted in order to avoid release of cargo. During these operations and also in connection with cargo hose handling at the manifold, it should be considered what kind of personal protection to be used. These considerations about personal protection should of cause also be taken during the normal cargo operation.

97 97 Gas- and vapour formation and distribution. Very intensive investigations on the behaviour of gases and vapours have been performed, especially on oil and product tankers, so that it should be possible to make a judgement on where and when dangerous gases might be present. In the following we will not distinguish between vapours and gases from oil products or chemicals but use the common word "gas". Loading into a gas free tank When loading a non-volatile cargo at temperatures well below the flashpoint there will be no flammable gas hazard. On the other hand loading a volatile cargo will have the effect that a certain amount of gas is evolved depending of the vapour pressure of the product. As a high vapour pressure cargo enters the empty gas free tank there is a rapid evolution of gas. Because nearly all gases are heavier than air, the gas forms a layer at the bottom of the tank which rises with the liquid surface as the tank is filled. Once it has been formed, the depth of the layer increases only slowly over the period of time normally required to fill a tank, although ultimately an equilibrium gas mixture is established throughout the ullage space. The amount and concentration of gas forming this layer at the beginning of the loading depend upon many factors, including: The true vapour pressure (TVP) of the cargo. The amount of splashing as the chemical enters the tank.

98 98 The loading rate The gas concentration of the layer varies with distance above the liquid surface. Very close to the surface it has a value corresponding to the TVP of the liquid. For example if the TVP is 0.75 bar the gas concentration just above the surface is about 75 % by volume. The gas layer depth varies of course also according to the circumstances. But normally the gas layer depth during loading will not be higher than 3 m when the TVP is less than 1 bar. A rather steep decrease in gas concentration is normal in the upper part of the layer so that only a relative small part of the tank atmosphere is between LFL and UFL and therefore flammable.

99 99 Loading into a non gas free tank Gas evolution after loading Venting the gas Gas evolution during discharging Before loading it must be expected, that the gas concentration is nearly the same all over the tank, and might very well be flammable. If the last cargo has been a very volatile product, the gas air mixture might be over-rich. Both the tank and the gas outlet must be considered dangerous. When the loading is completed and vent system closed the evaporation will continue until the equilibrium gas mixture equal the TVP has been established. During the voyage further evaporation might take place due to climatic changes with increasing temperature of the liquid. The amount of gas which has to be vented during loading depends on the evaporation rate and the loading rate. The composition of the vent gas is dependant on the position of the gas layer in the tank. When loading into a gas free tank the vent gas at the beginning will be nearly clean air. During the loading the gas concentration increases and during the final part of the loading toxic and flammable vent gas is to be expected. Gas concentrations from 30 to 50 % or even more with high vapour pressure cargoes are not unusual during the end of the loading and when topping off. If loading is performed into dirty or non gas free tanks, dangerous vent gas must be expected during the whole loading period. When a product is discharged from a tank, the same volume of air has to be introduced into the tank through vent openings. The incoming air dilute the gas in the tank by turbulence and eddies whereby the gas concentration decreases. During and after discharging a non volatile cargo, only small gas concentrations in the tank is expected unless the cargo has been heated during discharging, in which case some evaporation might occur. During discharge of volatile products, some constant evaporation from the liquid surface occurs and due to turbulence in the tank the whole tank atmosphere might become flammable. This flammable tank condition might very well be present during the whole discharge period. Discharge rate seem to be of minor importance to the gas concentration. After discharge the whole tank atmosphere is to be considered explosive, or at rare occasions overrich. Inerting during discharging assure a safe tank condition.

100 100 Gas evolution during introduction of water into the tank Gas dispersion If water is introduced into the tank through the cargo lines it must be anticipated that also gas might enter the tank, even though tank cleaning and line flushing has been performed. The gas might be present as a relatively thin layer on top of the water surface. Investigations during the latest years has considerably increased the knowledge of how gas is dispersed and diluted to non flammable and non toxic concentrations. Situations to which special attention has been paid are those where outlet of gas might present a potential risk to the crew and the ship. E. g.: a: Gas evolution during loading and ballasting. b: Outlets from P/V valves especially during the loaded voyage. c: Gas evolution and outlet when tank cleaning. d: Gas freeing and tank ventilation. e: Disconnection operations. The investigations has revealed that flammable and toxic gas may exist in a considerably larger distances from outlets than assumed earlier. Furthermore the investigations has shown that the greatest gas concentrations are met when topping off with open ullage holes, and that the largest gas volumes discharged to the atmosphere are during gas freeing. There is a potential danger of fire if the flammable gas zone reaches any location where there may be sources of ignition such as: a: The cargo deck which, although it is usually regarded as free of sources of ignition, is a work area. b: Superstructures and deckhouses which the gas can enter through doors, ports or ventilation intakes. c: An adjacent jetty, the ship's side and the water surface about the ship where boats with ignition sources might enter.

101 101 fig. 1 fig. 2 fig. 3 fig. 4 Gas distribution when one tank is being topped off. Three tanks being topped up Loading from lighter. Discharging to lighter fig. 5 fig. 6 Topping off at low tide Problems at shore during topping off Investigation conditions: alm wind. igh vapour concentration (50 %). Test chemical: Pentane. Wind speed Dilution of vent gas is directly dependent on the wind speed. But experience at terminals seems to suggest that at wind speeds above about 5 m/s dispersion is sufficient to avoid any flammability risk, when venting through the designated vent stacks. At lower wind speeds caution should be observed as the dispersion might further be complicated because the direction and location of the gas movements are not always predictable.

102 102 In calm weather the density of the gas is important and dangerous gas concentrations should be suspected at low places on deck, along the ship's sides and on the water surface. Regulations for tank vent systems Open venting: ontrolled venting: According to the IB-code special regulations for vent systems has been laid down for chemical tankers. All tanks should be provided with a vent system appropriate to the cargoes the ship is certified to carry. ommon gas outlets are only acceptable if the vapours from the carried products cannot react with each other in any way. IMO distinguish between different tank vent systems. Open venting either through ullage openings or through open pipings is allowed only for products with a flashpoint above 60, and not offering a significant inhalation health hazard. ontrolled venting system require pressure/vacuum valves on the vapour line from each tank and might either be completely independent or connected on the pressure side into common header or headers with due regard to cargo segregation. Valves in the vent system are not accepted, but by-pass valves are allowed for certain operations. Gas outlets should be positioned at least 6 m (4 m if the ship is built before 1. january 1994) above the weather deck or above the raised walkway if fitted within 4 m of the walkway. If high velocity vent valves with a minimum discharge velocity of at least 30 m/s pointing the gas stream upwards are fitted the height of the vent outlet might be reduced to 3 m. Outlets should be positioned at least 10 m from any air intakes or openings to accommodation, service and machinery spaces and ignition sources. Toxic products might require larger outlet heights and distances. Requirements are given in IB code Safety relief valves are required only on pressure tanks on ships carrying special products with high vapour pressure.

103 103 PRES-VA igh speed valve Item Description 1 ouse 2 Adapter 3 Pressure disc 4 Pressure seat 5 Booster 6 Booster Sleeve 7 Sleeve 8 Weight loading 9 Stem 10 heck lift 11 Vacuum house 12 Vacuum disc 13 Vacuum seat 14 Filter element 15 Venting cover 16 heck lift Gas freeing after tank cleaning Ships with IG system: Ships without IG system: After tank cleaning it might be tempting to open the tank hatches and tank cleaning openings believing that this would contribute to a faster or a natural gas freeing process. This is however an unsafe and dangerous method, unpredictable amounts of gas might be present on the deck area for a long time and the tanks are completely unprotected from ignition sources. SOLAS prescribe in hapter II-2 reg. 59,2 (reg for ships built after 1 July 2002) how purging and/or gas freeing of cargo tanks should be performed. Purging with IG until the gas concentration is below 2 vol. % before purging with air. 1. Venting with air through vent outlets positioned as described above. 2. Venting with a vertical vent velocity of at least 20 m/s through openings positioned at least 2 meters above deck level and furnished with flame screens. When the gas concentration is measured below 30 % of LFL tank hatches etc. might be opened. IB chapter 8.5 also gives the requirements to gas freeing in chemical tankers

104 104 Personal safety In addition to fire and explosion hazards crew members working on the tank deck should be aware of the possible presence of harmful gases during the different cargo operations. Personal safety protection equipment should always be used whenever the slightest possibility of personal contact with the cargo or harmful gases exists e. g. when taking samples, ullage and temperature measurements, or connecting and disconnecting hoses. When standing at open hatches, don't stand with the wind on your back as gas eddies might be formed on your front side and eventually inhaled. Positioning at open hatches Vapour ontrol Systems In stead of just releasing the gas evolved during loading, resulting in air pollution it is possible to divert the gas back to the terminal for further processing. Some of the products mentioned in IB chapter 17 require the ship to be equipped with a vapour return system but the code itself does not in details specify the technical construction of this system. From 1990 USA has regulated this subject and the rules will of course have an influence on the tank ventilation and the vapour return system. In the following the American rules are summarised:

105 105 These regulations apply to oil- and chemical tankers. The regulations are found in ode of Federal Regulations title 46 part 39, abbreviated to 46 FR 39, and deal with Vapor ontrol Systems (VS). Please note that these regulations do not apply to gas tankers. The regulations demand personnel who are in charge of operations involving VS to have participated in a training program covering the VS of the particular ship. The education or training shall include exercises and/or demonstration of the system installed on the ship covering normal operation and emergency procedures. The training program must as a minimum cover the following: Purpose of a vapor control system; Principles of the vapor control system; omponents of the vapor control system azards associated with the vapor control system oast Guard regulations in this part Operating procedures, including: Testing and inspection requirements, Pre-transfer procedures, onnection sequence, Start-up procedures, Normal operations; Emergency procedures. In 46 FR 39 there are several requirements regarding design and capacity of the Vapor collection System which will be too extensive to deal with in this course manual but some of the interesting points are: The vapor collection piping must be permanently installed, with the vessel's vapor connection located as close as practical to the loading manifold Incompatible vapors must be kept separate throughout the entire vapor collection system Vapor collection piping must be electrically bonded to the hull and must be electrically continuous An inerted tankship must have a means to isolate the inert gas supply from the vapor collection system An isolation valve capable of manual operation must be provided at the vessel vapor connection. The valve must have an indicator to show clearly whether the valve is in the open or closed position The last 1.0 meter of vapor piping before the vessel vapor connection must be: Painted red/yellow/red with the red bands 0.1 meter wide, and the middle yellow band 0.8 meter wide; and labeled ``VAPOR'' in black letters. Each vessel vapor connection flange must have a permanently attached 0.5 inch diameter stud at least 1.0 inch long projecting outward from the flange face. This stud fits into a hole in the hose flange and should thus prevent a liquid hose from being connected to the vapor system.

106 106 Vapour Manifold Presentation flanges, Orientation and labelling (from ISGOTT) Each cargo vapor connection must be determined for each cargo handled by the vapor collection tank of a vessel that is connected to a vapor collection system must be equipped with a cargo gauging device which provides a closed gauging arrangement and must be equipped with an intrinsically safe high level alarm and a tank overfill alarm. The VS must be capable of discharging cargo vapor at 1.25 times the maximum transfer rate The VS must have pressure sensors giving alarms at a high pressure of not more than 90 percent of the lowest pressure relief valve setting in the cargo tank venting system. The pressure drop through the vapor collection system from the most remote cargo tank to the vessel system at the maximum transfer rate and at lessor transfer rates. This drop in pressure must be included in the vessel's transfer procedures as a table or graph showing the liquid transfer rate versus the pressure drop. A cargo tank must not be filled higher than 98.5 percent of the cargo tank volume; or the level at which an overfill is set. A cargo tank must not be opened to the atmosphere during cargo transfer operations except as for gauging or sampling while a tank vessel is connected to a vapor control system unless certain requirements given in 46 FR g (1 4) are complied with. The above were extracts from the most essentially regulations but it is highly recommended to acquaint oneself with the regulations and be sure to fulfil the requirements regarding training in the system of the particular ship.

107 107 argo calculation In many countries the international system of units known as the SI-system has become national law. In the shipping and oil/chemical industry we still work with a number of systems and even with combinations of these systems. In any cargo calculation it is therefore essential to ensure that the units applied are used correctly. The idea of cargo calculation is in principle to find the mass of the cargo by using the following relation: m = dens. V, where m is the mass, dens. is the density and V is the volume. As these items can be expressed in several ways, it is essential in each circumstance to make clear how their connections are. Density Relative Density To state the density of a chemical the units of the SI-system are used i.e.: 1 meter for length and 1 kilogram for mass. The density which is defined as mass pr. unit of volume will thus get the unit [kg /m 3 ]. Due to the chemical's big coefficient of thermal expansion the density of a product shall always be given at a certain temperature. For chemicals it is normal to state the density at a temperature of 15 (or 20 which was normal some years ago). If the density is not given from the terminal it can be determined by means of a hydrometer. Besides the "absolute density" two other indications are sometime used, and that is Relative Density (Specific Gravity) and API-Gravity. is defined as: Rel.Dens t 1 /t 2 = Mass of x m 3 product at t 1 Mass of x m 3 water at t 2 As it is seen there should always be given 2 temperatures after Relative Density before it has any value. The Relative Density is of cause an abstract figure and it has therefore to be converted to density when you will have to use it to find the mass. The conversion is simply done by multiplying Rel. Dens. by the density of water at the temperature which is stated in the Relative Density. Then we have: Density at t 1 = (Rel. Dens t 1 /t 2 ) (density of water at t 2 ) In order to use this formula knowledge of fresh water density is a necessity and the following table shows FW density at the most common temperatures:

108 108 Density of Fresh Water in kg/m 3 : 0 : : : : F: : : Example 1: Relative Density 25/20 = Find density 25. From the table above the density of water at 20 is: kg/m 3. The liquid's density at 25 = kg/m 3 = kg/m 3 API Gravity is only used when handling oil products, but if you should encounter it, API Gravity may be transferred into Relative Density as follows: 141,5 Rel. Dens. 60/60 F = (API Gravity 60 F) + 131,5 and then it can be transformed into Density. The three different ways to give "density" can also be transformed mutual by means of ASTM table 3 and table 21 which is found in Volume XI. An extract from this table is shown below: API GRAVITY TO RELATIVE DENSITY AND TO DENSITY API RELATIVE DENSITY API RELATIVE DENSITY API RELATIVE DENSITY GRAVITY DENSITY GRAVITY DENSITY GRAVITY DENSITY (60 DEGF) (60/60 DEGF) (15 DEG) (60 DEGF) (60/60 DEGF) (15 DEG) (60 DEGF) (60/60 DEGF) (15 DEG) Volume: We normally talk about two different kinds of volume in the tanks and that is Gross Observed Volume and Gross Standard Volume. Gross observed volume Gross standard volume (GOV) - is the Total Observed Volume (TOV) less free water (FW) and bottom sediment, being the measured volume of product and sediment & water (S&W) at observed temperature and pressure. (In practice, GOV is usually calculated with no deduction for bottom sediment if any, which is very difficult to quantify). (GSV) - measured volume of product and S&W at standard conditions of 15 and atmospheric pressure. In practice, the GSV is the GOV multiplied by the volume correction factor (VF) obtained from the appropriate ASTM/IP Petroleum Measurement Tables.

109 109 The notions for volumes are often understood different in the different parts of the chemical business, so therefore it is essential to make clear to other people what you mean. Weight in air/ Weight in vacuum When handling pure oil products we often meet the problem whether the amount of cargo is given as "Weight in air" or Weight in vacuum". The weighing of oil products was in former days based on weighing the oil on a pair of scale against brass weights with a fixed density (around 8000 kg/m 3 ). The weight thus determined in air is due to the difference between the buoyancy of air on the light oil (about 850 kg/m 3 ) and the relatively heavy brass not identical to the "mass" (weight in vacuum). The difference between "Weight in air" and Weight in vacuum" depend on the density of the product and is : Densities from 500 kg/m 3 to 1134 kg/m 3 difference 1.1 kg/m kg/m 3 to 1802 kg/m kg/m kg/m 3 to 2456 kg/m kg/m 3 For the most common products the difference is thus 1.1 kg/m 3. alculated in the SI-units you will get: Density (in air) = Density kg/m 3. The density found in this way is often called "air corrected density". Methods of cargo calculation alculation of mass when the density is known at the cargo temperature alculation of mass using the density correction factor To determine the mass of the cargo by the earlier mentioned formula: Mass = Density Volume, the density and volume must be given at the same temperature. In principle it doesn't matter which temperature is used. The density is given at the relevant temperatures, - perhaps from a table. alculations are simply done as: Mass = Density Volume, using the density corresponding to the cargo temperature. In the chemical trade it is often normal to get information about a so-called "Density orrection Factor", which we here call β. This coefficient is used to change the density given at the standard temperature (s) to what the density will be at the temperature at which the volume is determined (t). (Be careful not to mistake this coefficient for the volume correction factor). The density conversion takes place according to the following formula: dens. t = dens. s - β Δ t

110 110 where dens. t is the density at temperature "t" (the actual temperature of the cargo in the tank), and dens. s is the density at the standard temperature (s),(normally 15 ). Δ t = t - s Please note that the density is decreasing at an increase in temperature contrary to volume, which increases with the temperature. Besides, there is the following connection between α and β: β s = α s density s where α s is the thermal coefficient of cubic expansion. Example 2: Volume and temperature are determined to respectively 1142 m 3 and Density at 20 is given as t/m 3 and "density corr. factor (ß) given as Find mass. mass = 1142 m 3 [ t/m ( )] = t. alculation of the mass of oil products (inclusive lube oils) by use of ASTMtables In the oil industry it is common to make calculations of oil-cargoes by means of a collection of tables issued by the American Society for Testing and Materials (ASTM). The tables are consisting of 14 titles where: Group 1. (Vol. I, II, III and XIII) are based on API gravity and 60 F Group 2. (Vol. IV, V and VI) are based on Relative Density and 60 F. Group 3. (Vol. VII, VIII, IX and XIV) are based on Density and 15. Group 1 and 3 are divided into four parts; one for crude oil, one for products, one for products with a known coefficient of cubic expansion and one for lubricating oil. Group 2 is only divided into three parts and that is one for crude oil, one for products and for products with a known coefficient of cubic expansion. Volume X of the tables comprises background, development and program documentation with the exception of programmes for the lube oil tables which are listed in the individual volumes. In the volumes XI/XII are found tables for conversion between volume measures, temperatures and density measures.

111 111 alculation when density is known at the standard temperature Normally we are informed about the density at 15. Then by means of table 54 (54 B for normal oil products and 54 D for lube oil) the gross observed volume is converted into the gross standard volume. Then the gross standard volume is multiplied by the density at the standard temperature. Example 3: In a tank with Base Oil (lube oil) the gross observed volume of the cargo is m 3 at a temperature of 3. The density is given from shore as 896 kg/m 3 at 15. alculate the mass and weight in air. 1. The observed volume is corrected to the standard volume at 15 by means of table 54D. A Volume orrection Factor found in the table is multiplied by the gross observed volume. TABLE 54D, GENERALIZED LUBRIATING OILS VOLUME ORRETION TO 15 DENSITY AT 15 TEMP TEMP. FATOR FOR ORRETING VOLUME TO Volume 15 = m 3 = m 3 2. Mass and weight in air is calculated: Mass = (896 kg/m m 3 )/1000 kg/t = t Weight in air = (896 kg/m kg/m 3 ) m 3 /1000= t alculation when density is known at a non-standard temperatur When we have measured or been informed about the density at a certain temperature in elsius degrees, table 53 (53B for products and 53 D for lube oils) is used to convert this density into density 15. Then the gross observed volume is converted into gross standard volume at 15 by using table 54 and the mass can now be found as: Mass (weight in vacuum) = Density 15 Volume 15. If we want to know the "weight in air" we use: "weight in air" = (density ) volume 15

112 112 Example 4: In a tank containing n-octane the liquid volume is measured as m 3 at a temperature of 3. The density is measured with a hydrometer as kg/m 3 at a temperature of 12. Find the mass and the "weight in air". 1. The observed density is converted into density 15 by using table 53B. Density 15 = kg/m 3 TABLE 53B, GENERALIZED PRODUTS DENSITY ORRETION TO 15 DENSITY AT OBSERVED TEMPERATURE TEMP TEMP. ORRESPONDING DENSITY AT The observed volume is converted into volume 15 by using table 54B. The "Volume orrection Factor" found in the table is multiplied by the observed volume. TABLE 54B, GENERALIZED PRODUTS VOLUME ORRETION TO 15 DENSITY AT 15 TEMP TEMP. FATOR FOR ORRETING VOLUME TO , Volume 15 = m 3 = m 3 3. Mass and "weight in air" is calculated: Mass = (702.8 kg/m 3 522,8 m 3 )/1000 kg/t = 367,4 t Weight in air = (702,8 kg/m 3-1,1 kg/m 3 ) 522,8 m 3 /1000 kg/t = 366,8 t

113 113 argo pumps and their use For use on board chemical tankers special pumps that fulfil the requirements in these ships have been developed. They should be able to pump both light and heavy products, and also they should be able to manage products with high vapour pressure and high viscosity. They should be made from materials resistant to a range of corrosive liquids. Pumping principles in general If the ship is carrying different incompatible cargoes at the same time it is necessary that these cargoes be separated completely. In many ships installing one pump with its own piping system in each tank has solved this problem. Such a submerged pump is called a deep-well pump and is a centrifugal pump. This solution also solves other problems e.g. the efficient stripping of the tank. In smaller ships with relatively few tanks the use of screw pumps located in a pump room is often preferred. The fundamental principle of the pumping of any kind of liquid falls into two distinct phases: 1. to move the liquid to the pump 2. to induce energy into the liquid in order to move it to the required destination. The first phase, moving the liquid to the pump, depends solely on the natural factors of liquid level above pump level and atmospheric pressure. The second phase is a matter of mechanics depending of the technical properties of the pump. owever, the second phase can influence the first since the extent to which atmospheric pressure is of value depends upon pump design and pumping conditions. Whilst no pump can reduce pressure at its suction to absolute zero in order to make use of the full atmospheric pressure of abt. 1 bar a well designed pumping system makes the fullest possible use of this pressure. The necessary pressure at the pump's suction side is described later in this chapter as the Nett Positive Suction ead (NPS). There are many types of pumps designed specifically for particular duties. In tankers the basic requirements are a discharge pressure at designed throughput in the range 6-15 bar ( p.s.i. (g)) and good suction performance. Marstal Navigationsskole April 14

114 114 Types of pumps Different types of pumps are used as cargo pumps in tankers. Generally speaking these pumps may be divided into three different main groups according to their working principle namely: 1. entrifugal pumps. 2. Displacement pumps. 3. Ejector pumps (eductors). These three groups of pumps are working quite differently and should of course be operated in a quite different manner. 1. entrifugal pumps are today the most commonly used main cargo pumps in tankers. You will see them as both one stage and multiple stage pumps. They are very suitable for pumping large quantities. The weight is small compared to the performance and they are not particularly sensitive to impurities and smaller particles in the product they pump. They are easily regulated and easy to drain and clean. 2. Displacement pumps move a certain volume at each cycle, the centrifugal pump does not, and this is the main difference between the two pump types. The centrifugal pump makes a certain pressure and the volume pumped is mainly determined by the head at the discharge side. The most well-known displacement pump is the reciprocating piston pump, but also the screw pump belongs to this category. 3. Ejector pumps have no mechanical moving parts, perform a good suction even when air enters the suction line, and they are not vulnerable to impurities and particles in the liquid. The best performance is achieved with no or at least very little head on the discharge side. On board larger tankers they are often used as stripping pumps. Marstal Navigationsskole April 14

115 115 entrifugal pumps In the following we refer to centrifugal pumps only. Other types of pumps will be dealt with later. In centrifugal pumps the motive force is provided by a rotating impeller which takes suction at its centre and flings the pumped liquid out into the casing from where it flows to the pump discharge. The head so generated, is dependent on the diameter, blade angle and speed of rotation of the impeller. Flow rate is affected by the pressure in the discharge system and can fall to zero. Reverse flow through the pump is also possible if a nonreturn valve is not fitted in the system. ead/quantity The pressure energy of a liquid being pumped is related to the speed of rotation of the impeller and, for a given speed, the head generated by the pump in meters is constant regardless of specific gravity. Also the volumetric discharge rate is independent of the gravity of the liquid. The relationship between head and pressure is expressed by the following formula. Pressure[Pa] ead[m] = Density[kg/m 3 2 ] 9,81[m/s ] The energy required to maintain the pump speed does, however, vary with density (or S.G.) of the liquid. It is thus convenient to illustrate pump performance with graphs of head in relation to quantity of throughput (known as head/quantity or.q. curves) for given pump speeds. The relationship between head and quantity is such that when the pump throughput is zero head is maximum (for example, when pumping against a closed valve). As throughput increases, the head decreases. On the.q. curve in the following figure is marked the "design" point. This indicates the condition of head and throughput at which the pump works at maximum efficiency for the speed indicated and will normally be the duty specified for the pump when it is ordered. The ideal.q. curve is a straight line whose slope is determined by the pump design. owever when certain losses (mainly friction) are taken into account, the typical curve as shown in the figure is obtained. The two.q curves on next page are from the same pump but at two different r.p.m. Marstal Navigationsskole April 14

116 116 Marstal Navigationsskole April 14

117 117 The basic characteristics of centrifugal pump can be expressed in the following mathematical formulas: Q 1 Q 2 = n 1 n 2 = Throughput varies as speed 1 2 = n 2 1 n 2 2 = ead varies as speed squared P 1 P 2 = n 3 1 n 3 2 = Power required varies as speed cubed These relationships may be used to approximate calculation of pump curves, but of course they are subject to appreciable modification by the system in which the pump is working. The following diagram shows the performance of a typical deepwell pump with two speeds possible. i.e r.p.m. and 1185 r.p.m. It is seen from the Q/ curves that this 33% speed reduction causes a max. head reduction from 140 mlc to only 60 mlc, (the max. head is reduced by nearly 60%). Power The power required for pumping varies with the circumstances. For a given pump-speed more power is required to pump high S.G. liquids than low. The power consumption is nearly proportional to the S.G. (density). The minimum power requirement is when the pump discharge is closed and head is maximum but throughput is zero. As throughput increases head falls but the power absorbed by the pump increases although a peak may be reached beyond which the power requirement again decreases. The pump is normally governed not to exceed its designed speed when power demand is low. owever, when operating under conditions where the power demand is high, the pump speed may fall because insufficient power can be supplied to maintain maximum revolutions but the pumping rate, because of low head, may, nevertheless, be very high. Depending on the motor type the pump may stop if the motor is overloaded. This is normally the result if the pump is electrically driven. In the diagrams also an efficiency curve is shown. It tells the ratio between delivered and absorbed power. When run most economically this pump makes use of a little less than 70 % of the power supplied by the electrical motor (shaft power). The NPS curve will be dealt with later. When using the.q. curve for practical purposes e. g. during discharging it is necessary to convert head in meters to pressure or vice versa as it is the pressure given in some pressure unit you read on the manometer. This of course is a little boring and some pump manufacturers have done this job already by drawing. Q. curves for different densities of the liquids to be Marstal Navigationsskole April 14

118 118 pumped. In the following diagram also different P curves have been drawn. Back pressure from shore From the previous discussion it is seen that a pump will work somewhere on its. Q. curve. Exactly where is decided by the pressure or head in the discharge line. It is possible to plot the pressure variation in the shore line into a diagram in the same manner and using the same units as with the. Q. curve thus producing a so called Shore curve. If the ship's.q. curve and the shore curve are superimposed in the same diagram the common point will decide the discharge rate Q and the head in that particular discharge situation. If the shore curve is steep it represents a discharge line with great resistance typically a long and narrow line and the discharge rate will be rather small with a high head. Marstal Navigationsskole April 14

119 119 The shore curves from the different installations are seldom delivered to the ship for information. More often a certain pressure is required at the manifold and this pressure, of course, also decides the discharge rate through the particular shore line system. The suction side The factors which cause liquid to flow to the pump are: 1. The pressure acting on the surface of the liquid in the tank (normally atmospheric pressure) and, 2. The liquid level in the tank relative to the pump suction. Since no pump can generate a total vacuum at its suction inlet, only a proportion of the atmospheric pressure can be usefully employed. Therefore, before a pump can operate satisfactorily a certain pressure must exist at the pump suction and this is known as Required Nett Positive Suction ead (NPS.), which is the minimum absolute pressure in excess of liquid vapour pressure which must exist at the suction inlet of the pump to ensure satisfactory operation (free from cavitation). The value of required NPS depends on pump design and is specified by the pump manufacturer. The diagram two pages ago illustrates a typical NPS curve. If the pressure at the pump inlet is lower than the NPS plus the vapour pressure of the liquid cavitation is the result. Small vapour pockets are formed near the centre of the pump as the liquid boils and these vapour bubbles are moved with the liquid outwards to a higher pressure where they implode very rapidly and by and by corrodes the metal of the impeller. This phenomenon is known as cavitation erosion. eavy cavitation sounds like pumping rubble stones. The best way to avoid cavitation is to use as short and direct suction lines as possible, and to mount the pump as low as possible. Submerged pumps in each tank using the deep-well pump principle best accomplish this. Marstal Navigationsskole April 14

120 120 If cavitation occurs, the pump speed should be reduced immediately. This will reduce the friction loss in the suction line as well as the NPS. If the pump speed cannot be reduced, flow should be regulated by partly closing the discharge valve. Deep-well pumps Deep-well pumps are often electrically driven. The earlier shown curve diagram is for such a multiple stage pump. The shaft bearings of these pumps are cooled and lubricated by the liquid surrounding the shaft. When the tank becomes empty the pump must be stopped, otherwise serious damage to the bearings may be the result, or worse, - an explosive atmosphere in the tank may be ignited. Basically there are no difference between single stage or multiple stage centrifugal pumps, they should be operated in the same way. If speed regulation is not possible the only way to reduce the flow, if this is desired, is to throttle on a suitable valve on the discharge line, or to stop the pump. Marstal Navigationsskole April 14

121 121 ydraulically driven deep-well pump If the pump is driven by a hydraulic motor it is always possible to regulate the speed. The following picture shows a widely used cargo pump in chemical carriers, the Framo pump. Motor and pump is as a single unit. It is placed as close to the tank bottom as possible at the end of the pipe stack consisting of three concentric pipes inside each other. The innermost pipe is the hydraulic pressure line, the next is the hydraulic return line and the outer pipe is an air filled cofferdam. The cofferdam ensures that the hydraulic oil under no circumstances comes into contact with the surrounding cargo. The cofferdam must be blown at suitable intervals with air or nitrogen to check that the system is tight especially the sealings at the pump glands. The discharge pipe is a separate line with discharge valve. After the tank has been emptied the pump is kept running, the discharge valve is closed and the line before the valve is pressurized with air or nitrogen thereby displacing the liquid downwards out and up through the small diameter pipe, which is connected to the main line after the now closed discharge valve. In this way it is possible to empty the discharge line to shore. Marstal Navigationsskole April 14

122 122 Screw pumps. A screw pump is a displacement pump and has to be operated quite differently from a centrifugal pump. The volume delivered is proportional to the number of revolutions and with viscous liquids almost unaffected by head and back pressure. Screw pumps have a very good suction ability and are even able to pump air or gas. They are very vulnerable to impurities in the liquid like threads, scale and other particles, which must be avoided. Normally filters are fitted in the suction line. They are common on smaller tankers and are especially suitable to highly viscous products, such as molasses and asphalt. The figures below visualize the working principle of different screw pumps. The Bornemann pump has two spindles and inlet from both ends. The outlet is from the middle of the spindles. As the discharge pressure could grow to nearly indefinite values if e. g. a discharge valve were closed a safety valve system is an important integrated part of the pump. Marstal Navigationsskole April 14

123 123 The following diagram is typical for a screw pump. urves for different viscosities are drawn and it is seen that the capacity as a matter of fact is better for high viscosity (thick) liquids than for low viscosity liquids like water, which is quite opposite compared to centrifugal pumps. The explanation is that the screw pump is not tight i. e. the rotors do not touch each other or the housing and some back flow is possible especially with thin liquids and high pressures. Marstal Navigationsskole April 14

124 124 The following diagram shows that the power consumption is proportional to back pressure, - another feature quite different from centrifugal pumps. The diagram below shows that a screw pump is able to deliver cargo against high differential pressures, compared to a centrifugal pump. (Differential pressure is the difference between the pump s discharge pressure and the pump s suction pressure) Marstal Navigationsskole April 14

125 125 Marstal Navigationsskole April 14

126 126 Performance diagram for various Bornemann screw pumps Marstal Navigationsskole April 14

127 127 andbooks and Literature The information which is offered in the IB-code will not always give a satisfactory idea of the dangers of the chemical. Neither the dangers nor the possible precautions are adequately described. Official codes and product lists. IMO: IMO: IMO: To get the essential information of the products, which are to be transported, it is necessary to consult handbooks, or Material Safety Data Sheets (MSDS) which gives enough information to get a complete indication of the dangers of the chemical and the precautions to be taken during transport. The best way to accumulate the information will be in a special hemical data Sheet. An example is shown at the end of this chapter. ode for the onstruction and Equipment of Ships arrying Dangerous hemicals in Bulk (B-code). International ode for the onstruction and Equipment of Ships arrying Dangerous hemicals in Bulk (IB-code). MARPOL Rules and Regulations from the lassification Societies. US oast Guard: ode of Federal Regulations (FR 46) US oast Guard: M.E.T. Publication #515 (Rules and Regulations for Foreign Vessels Operating in the Navigable Waters of the United States) Arbejdstilsynet: Grænseværdier for stoffer og materialer. (Danish list of TLV s). AGI: TLVs and BEIs andbooks and Safety Guides. IS: IS/OIMF: IMO: awley s: US oast Guard: Verwey: Dräger: hemserve: ommel: Tanker Safety Guide (hemicals) International Safety Guide for Oil Tankers and Terminals (ISGOTT) Medical First Aid Guide. ondensed hemical Dictionary. hemical Data Guide for Bulk Shipment by Water Tank leaning Guide. Detector Tube andbook MIRALE, Tank leaning Guide andbuch der Gefärlichen Güter. Marstal Navigationsskole April 14

128 128 awley s: ondensed hemical Dictionary. Acrylonitrile. (propenenitrile; vinyl cyanide). AS: :N. 40th highest-volume chemical produced in U.S. (1995) Properties: olorless, mobile liquid; mild odor. Fp 83; bp , d (25), flash p 32F (0) (TO). Soluble in all common organic solvents; partially miscible with water. Derivation: (1) From propylene oxygen and ammonia with either bismuth phosphomolybdate or a uranium-based compound as catalysts; (2) addition of hydrogen cyanide to acetylene with cuprous chloride catalyst; (3) dehydration of ethylene cyanohydrin. azard: Toxic by inhalation and skin absorption. A carcinogen. Flammable, dangerous fire risk. Explosive limits in air 3 to 17%. TLV: 2 ppm, suspect of carcinogenic potential for humans. Use: Monomer for acrylic and modacrylic fibers and high-strength whiskers: ABS and acrylonitrile styrene copolymers; nitrile rubber; cyanoethylation of cotton; synthetic soil blocks (acrylonitrile polymerized in wood pulp); organic synthesis; adiponitrile; grain fumigant; monomer for a semiconductive polymer that can be used like inorganic oxide catalysts in dehydrogenation of tert-butanol to isobutylene and water. Marstal Navigationsskole April 14

129 129 U.S. Department of Transportation United States oast Guard hemical Data Guide for Bulk Shipment by Water Marstal Navigationsskole April 14

130 1. Product name 2. hemical Formula 3. hemical Family / Pollution ategory 4. UN No. / AS number 5. IMO ode Requirements (Ship Type Etc.) 6. IMO Special Requirements (ol. "o") 7. Treshold Limit Value / Odour Threshold 8. Liquid Density / oeff. of cubic expansion 9. Relative Vapour density / Vapour Pressure 10. Flashpoint / Auto Ignition Temperature 11. Flammable Limits 12. Melting Point / Boiling Point 13. Viscosity / Static Accumulator, - yes or no? 14. Reaction with Water 15. Solubility in Water 16. Reaction with Air 17. Reaction with other Substances 18. Self Reaction 19. Segregation Requirements (USG) 20. ealth azards/usg health hazard rating 21. Personal Protection Equipment 130 EMIAL DATA SEET 22. First Aid Eyes Skin Inhalation Ingestion 23. Fire Fighting 24. Toxicity when at Fire 25. Spill ombating 26. oating Restrictions 27. Special Information Marstal Navigationsskole April 14

131 131 Special argoes Precautions in relation to extremely corrosive liquids When handling corrosive liquids especially three danger details should be born in mind: 1: Danger of corrosion of ship or equipment. ommon ship-building materials will be corroded pretty fast and many of the products in this group can only be transported in ships equipped with special tankmaterials, special coating and with gaskets used to the purpose. It is important to check if the concentration of the product has in influence to the resistance of the materials. 2: Danger of fire: When corrosive liquids attack metal, fumes are evolved which may be flammable or explosive if mixed with air. Especially acids evolve free hydrogen, which is very explosive mixed with air, and do not forget that corrosive liquids themselves may be flammable and may cause auto ignition in saw dust, rags or other similar materials. 3: ealth hazards. The liquids will when they come in contact with skin or tissue damage or even destroy this. The wounds, which come, will be painful and heal slowly. Eyes and mucous membranes are very sensitive to corrosive liquids, so therefore do not neglect the use of protection equipment. Tank cleaning after corrosive products may require quite special procedures and relevant tank cleaning guides should be consulted. Precautions when handling very reactive chemicals The products in this connection can be split into several groups i.e: 1: Liquids with a self-reaction. There will normally be two kind of reactions in question and that is decomposition or polymerization. Both reactions may be catastrophic to the ship, and when transporting such liquids it is important to monitor the temperature of the cargo at certain intervals. A rise in temperature may indicate that a reaction is in progress, and some measures should be taken to bring the situation under control. Decomposition will also cause heavy rise in pressure. Such liquids will normally be added an inhibitor and may require inerting, and the shipper should give a clear loading instruction and voyage-instruction in relation to control of inhibitor and eventually addition of extra inhibitor. Marstal Navigationsskole April 14

132 132 2: Liquids which react violently with water. Many chemicals cannot come in contact water unless it causes violently reactions. The reaction may be decomposition with formation of enormous amounts of dangerous fumes; it may be formation of acids or salts with hydrogen evolution, and there may be an undesirable temperature rise. Other reactions can cause discolouration of the product or may form other materials, which may attack the coating or tank materials. Information about reactions can be found in handbooks. 3: Liquids which react with air. As many products may react with air it will often be necessary to inert the tanks. The grade of inerting depends of the product and its purity. It may be assumed that the shipper will give accurate instructions about the inerting and whether traditional inert gas or pure nitrogen may be used. 4: Liquids which react with other chemicals. ow far some of the products that are to be loaded can react with each other, shall often be considered on board, even if it may be expected that the shipper will give information about this problem. The best guide to this problem is US oast Guard ompatibility hart, but the information from this compatibility chart should also be compared with the information from the shipper's data sheet. arriage of vegoils (edible oils) NIOP and FOSFA FOSFA lists of cargoes It is a sad fact that a number of cargoes are contaminated by remnants of the previous cargo carried in a ship s tank, despite thorough and conscientious cleaning prior to loading. This naturally creates a serious problem whatever cargo is contaminated, but becomes even more serious when the cargo is meant for human consumption. The National Institute of Oilseed Products (NIOP) in the USA, and the Federation of Oils, Seeds and Fats Association (FOSFA) in the UK have both conducted studies and research in order to eliminate the potential contamination problem. Discussions have taken place with representatives of importers and some shipowners in this connection, and cargo lists have been prepared. FOSFA gives a list of so called Banned immediate previous cargoes with more than 50 products and a list of Acceptable previous cargoes giving about 110 different cargoes which can be accepted as previous cargoes. Marstal Navigationsskole April 14

133 133 Acceptance procedure European Union onclusion Discharging Before a ship can be accepted as carrier of edible oils it shall comply with the FOSFA International Qualifications for all Ships Engaged in the Ocean and Short Sea arriage and Transhipment of Oils and Fats for Edible and Oleo-hemical Use giving requirements mainly to materials of construction and tank coatings. A statement, in the form of the FOSFA International Ship s Qualifications ombined Master s ertificate signed by the ship s captain/chief officer shall be provided for the shipper, certifying that the ship is qualified for the coming voyage with edible oil. The ship must also comply with the FOSFA International Operational Procedures for all Ships Engaged in the Ocean and Short Sea arriage and Transhipment of Oils and Fats for Edible and Oleo-hemical Use which for example details the requirements to the previous cargoes. It is worth noting that in order to accept a cargo as Acceptable Previous argo it shall have been not less than 60% by volume of the tank! The Operational Procedures will also give details such as inspection of tanks, sampling, heating instruction and loading through shore hose directly into ship s tanks. When trading to or between members of the European Union special regulations apply. They are much similar to those of FOSFA, but are stricter as regards the requirements to previous cargoes. It is hoped, by following the standards given by the recognised organisations, that cases where cargoes meant for human consumption are contaminated can be avoided. Mostly the same precautions should be taken during the discharge as during the loading. Again it is important to check the function of P/V-valves. At the very start of the discharge emergency stops should be tested. If the tanks have been filled above the level of the highest high-level alarm, all tanks should be discharged to a level below the high-level alarm in the beginning of the discharging operation, thus allowing the alarm to be put into operation, and giving the possibility of a warning if a leaking valve in the system causes a tank to be filled during the discharge of other tanks with the same product. Sometimes it is not allowed that air is drawn into the tank during discharge, so in order to prevent vacuum the tanks must be refilled with inert gas or nitrogen. This is not a Marstal Navigationsskole April 14

134 134 problem in ships with their own inert gas generator, but in other ships it will be necessary to connect a vapour return or a nitrogen source from shore. During the discharge it is necessary to be aware of the conditions in the pump room, if any. Even if the pumps can be run from outside the pump room it is sometimes necessary to enter the pump room to inspect the pumps or valves there. Despite the operation of mechanical ventilation, it must be a standing order, that nobody enters the pump room without permission from the responsible officer. This officer is the one to decide whether to use protective equipment and moreover assure that the regulations for entering the pump room are adhered to. Ballasting It might be necessary to use uncleaned cargo tanks containing residues as ballast tanks. This is not permitted in tanks which have contained water reactive chemicals, as well as it is of cause only allowed to ballast in accordance to the regulations in MARPOL's ANNEX II. If tanks, which have contained flammable or toxic cargoes, are used as ballast-tanks, it must be remembered that a lot of vapour is released when taking ballast into these tanks. The local regulations on air pollution should also be consulted in this situation. Marstal Navigationsskole April 14

135 135 Let this chapter start with an article written by a representative from IVER Ships. This article speaks for itself and covers many of the dilemmas concerned with the transport of cargoes on board chemical tankers. Tank leaning (from Iver Ship s web site) From then till now. Since tankers were first developed there has been the problem of how to effectively clean the vessels tanks before loading the next cargo. In the first half of the 20th century tanks were mainly cleaned by a high pressure hose man handled by a sailor. This was dangerous work as the gas in the tank together with the slippery surface led to many accidents. The first breakthrough came with the development of the tank cleaning machine. This in effect was a heavy-duty garden sprinkler, which could be lowered into the tank on the end of a hose. The water pressure was, via a gearing mechanism, used to slowly rotate the machine and at the same time rotate the outlet nozzles. This meant that all tank surfaces were exposed to the full blast of the water and ensured consistent cleaning results. At the same time the cargo pump stripped away the wash water and transferred it to a slop tank. As no personnel were required to enter the tank higher temperatures could be used for the wash water thereby increasing the cleaning effect. These machines and their hoses are however heavy to handle and most ships today have the machines mounted permanently inside the tank. These greatly speed up the tank cleaning operations and make it safer too. The tank can be kept fully closed during cleaning, thereby reducing the crews exposure to cargo vapours. All new tanker vessels today are built with a double hull and this allows the inside of the cargo tank to be smooth sided. In effect one hull is built within the other and all the structural strengthening steelwork is contained in the spaces between the two hulls. Smooth sided tanks are a lot easier to clean. Modern vessels with good equipment can perform tank cleaning safely and effectively and compliance with regulations ensures an absolute minimum impact on the environment. owever cleaning tanks for certain chemical cargoes requires a lot of expertise and hard work. A precise view of an imprecise science. Our business depends on being able to load our vessels with many different cargoes, sometimes at very short notice. In order to do this, we have to be able to clean our vessels quickly, efficiently and better than our competitors. Easy if you know how, and even easier if you understand a few basic principles? Tank cleaning does not play by any rules. What works one time will not give the same result the next. It can trick you, drive you crazy and sometimes it can even make you smile! It does without doubt fulfil the definition of an imprecise science. What is successful tank cleaning? So how are we managing to stay ahead of the field? Very simply, by knowing when to stop cleaning. This makes light of a very complex set of situations, but this is fundamentally the essence of successful tank cleaning. If you clean 'too short' then the vessel is not clean enough and the likelihood is tank rejection. Marstal Navigationsskole April 14

136 136 If you clean 'too long' then you risk damaging the coated internal surfaces of the cargo tanks. You will waste time and money, cause crew fatigue and still run the risk of tank rejection. Over cleaning can lead to just as many problems as under cleaning. But still a rejection is a rejection. Fundamentally though, tank cleaning is largely common sense. It follows the same principles of washing plates and cutlery after you have eaten dinner. If you keep the plates wet by soaking them in water, they are far easier to clean in the morning compared to leaving them on the dinner table overnight. If you have oil or grease stains, use a mild detergent to remove them, because water on its own is almost ineffective. If the plates are still dirty after the first cleaning, you have to do them again, but it is usually more difficult because the residues have had a chance to dry out. Time It follows, that time is certainly of the essence here and it is fair to say that if you have an unlimited amount of time, then any job is possible. But consider the enormous costs of running a vessel for just one day. It becomes very apparent that saving even a few hours can, and will, make a difference to the voyage. If we take too long to clean a vessel then an alternative carrier will be sought, who takes less time. So we lose not only our reputation but also dollars and cents in terms of lost freight. So getting the job done quickly and effectively the first time would seem to be the key to keeping us ahead of the competition. This will also secure the reputation of the company in the eyes of our clients, without whom, we would not have the business to do. Tank inspection So if it is that easy, then why is tank cleaning always the bottleneck in the process? After all, if we could just arrive in port every time, fill up and head off for the destination without any delay, then there would be no worries! Everybody would be happy and the perfect logistic process would be just around the corner! The reason is the inspection process and satisfying the requirements of the load port cargo tank survey. This survey is carried out to verify that the vessel meets pre-set quality specifications. This result of the survey tells everybody involved in the shipment that the tank cleaning has been carried out to a certain standard. In essence the difference between loading petroleum products (PP) like gas oil or gasoline and fine chemicals like methanol is in the inspection process. PP products are loaded on a visual inspection, in other words the tank has to be visually empty and clean. For fine chemicals a wall wash test of the tank surface is carried out. This means that the tank not only has to be visually clean, it also has to be chemically clean as well. Although wall wash tests performed on the tanks are precisely defined there are many variable factors that can influence the outcome. Weather conditions, standard of test equipment, sample containment and not least, surveyor expertise can all affect the final outcome. Reaching these pre-set wall wash standards can and does cause enormous problems and this is what causes the delays. onsider that the vessel is floating in seawater containing approximately 33,000 ppm (parts per million) of salt, and the usual wall wash specification prior to loading methanol is 2 ppm! As a way of understanding how small one part per million is, consider this comparison: One second in 11 ½ days!! To improve our vessels ability to pass these tests our vessels are now using relatively high-tech laboratory instrumentation to accurately monitor tank-cleaning Marstal Navigationsskole April 14

137 137 operations. oupled with ship's staff expertise and a lot of hard earned experience we are able to continually expand our cleaning capability. Our on board laboratory enables the vessels' officers to accurately know when to stop tank cleaning and in certain cases, what to do next. This in turn takes the word guessing out of the whole process. It is still not an exact science but our procedures ensure that our tank cleaning results are not a lottery; they are more of a certainty. With this approach we have been able to significantly improve our tank cleaning capability and reduce down time and tank rejection. Marstal Navigationsskole April 14

138 138 Tank leaning Operation leaning of cargo tanks in connection with the transport of liquid chemicals in bulk calls for special considerations, which may be quite different from oil transport. It must be taken into consideration, which product has been in the tanks and which products are to be loaded. Furthermore it is of importance, which equipment is at hand and how much time is available. leaning from and to chemical cargoes can be both time consuming and expensive. In all cleaning operations it is essential to remember that all safety rules must be strictly adhered to. The actual cleaning operation will almost invariably follow the flow diagram shown below, as the same questions will arise each time. Flow diagram The details of the flow diagram are explained below. EMIAL TANKER LEANING Same argo? If the vessel is to carry the same product on the following voyage, the cleaning operation might be omitted. Of course this is not always the case, as there still may be a number of reasons for the shipper to demand clean, gas free tanks before loading. One such reason might be that the final use of the product is quite different. Marstal Navigationsskole April 14

139 139 igh Vapour Pressure? If the vapour pressure of the product exceeds 50 mb at 20, tank cleaning may be accomplished simply by ventilation according to MARPOL's Annex II. Whether this is an efficient technique or not depends on the product and the vessel's equipment. For example it is possible and allowable to ventilate pure Benzene, but it might be unwanted because of the toxic properties of Benzene vapour, and because of remaining smell and/or solid residues in the tank. Tank cleaning by ventilation alone requires efficient blowers and MARPOL specifies a minimum blower capacity according to the diameter of the air and the depth of the tanks. Tank cleaning by ventilation is an excellent procedure with many igh Vapour Pressure Products, as it eliminates the need to decide what to do with slops. The method is particularly efficient if the vessel features a hot air or dry air system. Prewash Annex II MARPOL's Annex II specifies a Mandatory Prewash for many substances. If this is relevant for the product to be cleaned, the procedures in the vessel's P&A-manual should be strictly adhered to. Mostly the above mentioned considerations will be dealt with quickly, and what is left is the actual tank cleaning where the purpose generally is to get the tanks as clean as possible, as the next cargo might not have been decided upon. Preliminary leaning For the first and, possibly the only cleaning, it must be decided whether to use water or not. A few cargoes will react with water (for example TDI) and form insoluble sediments. For the great majority of cargoes there is, however, no doubt - the tanks are washed with water. The purpose of pre cleaning is to remove the residues after the discharge. The sooner the pre cleaning is carried out after discharge, the easier oil and residues will be removed. Pre cleaning should be done with tank cleaning machines using sea- or fresh water. Temperature for pre cleaning depends on the grade of cargo previously discharged, but the wash water temperature should normally not be more than 10 higher than the cargo previously discharged. This procedure has to be executed with a view to obtain optimal results in cleanliness and is not set up in respect to MARPOL. The next question will be whether to use hot or cold water, and this might well be the most important question. With many products a wrong choice of washing temperature will not mean a lot, but when cleaning after a "drying oil" (veg- and animal oils with a low content of free fatty acids) it is of utmost importance to start with cold water as the product otherwise will dry into a coat on the tank surfaces which is very difficult to remove. Using hot water will also be a great mistake after many polymerisable products. If in doubt consulting various Tank leaning Guides, Survey ompanies or the shipper might give a suggestion, and if it is impossible to get enough information the washing procedure should be initiated with cold water. Below is shown a list of some vegetable oils and animal oils. Marstal Navigationsskole April 14

140 140 Vegetable and animal oils Low acid value igh acid value old water old water ot water Drying oils Semi-drying oils Non-drying oils Mustardseed oil Babassu oil Palm oil hina wood oil andle but oil Almond oil Fish oil orn oil Arachis oil empseed oil otton seed oil amphor oil Linseed oil roton oil anaga oil Menhaden oil Fish oil ashew nut oil Oiticica oil erring oil astor oil Perilla oil Maize oil oconut oil Safflower oil Poppy seed oil od liver oil Soyabean oil Sesame oil Ground nut oil Tall oil Sunflower oil Lard oil Tung oil Wheat oil Neatsfoot oil Walnut oil Olive oil Peanut oil Pine oil Rape seed oil Sperm oil Tallow oil Whale oil Furthermore it must be decided how long the washing should go on. The time will always depend on the ship's equipment, and might vary from one cycle to several hours depending on the tank structure, the product and the washing machines. Again reference to a Tank leaning Guide might be useful. Tank leaning Guides Several companies, which manufacture cleaning agents, also publish handbooks or instructions to explain how to use the cleaning agents for various products. Also some independent companies publish such tank-cleaning guides. An example of such a guide is the Tank leaning Guide published by Laboratory Dr. A. Verwey, Rotterdam. This guide takes both the discharged cargo and the product to be loaded into consideration. The list advises on the cleaning operation between 415 different products. Below is shown a copy from the first part of the book which provides a cleaning code by entering with the products in question. Marstal Navigationsskole April 14

141 141 In the second part of the book the cleaning codes are translated into a cleaning operation and a copy from this part of the book is shown bellow. Marstal Navigationsskole April 14

142 142 The cleaning guide should only be used as a recommendation, as no consideration is given to the coating, piping materials etc. Such problems should be carefully considered and incorporated into the cleaning method chosen. The most important answers to be found in a cleaning guide are: 1. Should the cleaning start with cold or hot water. 2. If we decide to use a cleaning agent - which type should be used and in which concentration. On the other hand the instructions in the guide regarding washing times are no more than an educated guess. The guide mentions a certain numbers of washing cycles but that is in fact a broad concept as the time for one cycle can vary from one type of washing machine to an other machine. Final leaning hemical additives There are a great many substances, which can be added to chemical cargo residues which work on the detergent principle and facilitate the tank washing procedures. This is especially true for water insoluble cargoes. These cleaning compounds consist of a synthetic soap, a detergent and an emulsifier, all dissolved in an aromatic or aliphatic hydrocarbon solvent. The synthetic soap and detergent activate cleaning while the emulsifier keeps the impurities dissolved in water. These are carried into the water insoluble residues by the solvent carrier. This is the most popular method of chemical cleaning and is known as emulsification. A second method of chemical tank cleaning is called saponification, a process which basically turns the residue into a soapy solution. This type of cleaning is ideal for animal and vegetable oils since they are esters and are composed of glycerols and fatty acids, which can be broken down by the alkali such as caustic soda. The fatty acids react with the caustic forming a soapy mixture, which is soluble in water. There are products on the market, which contain a quick break emulsifier thereby reducing the amount of tank washing. These emulsifiers ensure a clean break between the emulsified residues and the wash water in the settling tank. The free water may have a residue content as low as 10 ppm and therefore may be removed from the settling tank for reuse. This way the amount of washing in the settling tank is kept as a minimum. The use of any type of chemical additive must have the approval of the tank coating manufacturers. This is usually done by the additive manufacturer prior to marketing his product. In addition to the variety of emulsifying solvents, saponifying agents, etc., there are a large number of other products available to the operator committed to coated tanks. These products include deodorizers, passivating paste for stainless steel, hydrocarbon dispersants, degreasants, etc. The operator must temper the manufacturers recommendations with his own experience. Additive quantities and concentrations stipulated by the manufacturers are sometimes on the high side and since none of these products are cheap it is advantageous to the operator to become familiar with each product so that an economical and effective point can be reached. Marstal Navigationsskole April 14

143 143 If it is considered necessary to perform further cleaning after the preliminary cleaning, more demanding techniques may be utilised. re 1: 1. Saponifying with caustics. 2. leaning with detergents 3. Dissolving with a solvent. 4. hemical reaction. 5. Steaming Vegetable and animal oils are easily saponified with an alkaline like austic Soda or austic Potash. The remaining soap from austic Potash is readily washed away with water whereas the soap from austic Soda tends to form hard brittle particles, which are almost insoluble in water. The schedule below can be used to determine how many kilograms of austic Soda necessary to obtain a required p value of the tank cleaning water. AUSTI SODA SOLUTIONS Tons of Kilogram of austic Soda water p 11.5 p 12 p 12.5 p 13 p 13.5 p re 2: re 3: After a cargo of mineral oil or its derivatives synthetic soaps or special cleaning agents which are mixtures of synthetic soaps (detergents) and other emulsifiers can be used for the final cleaning. Some cleaning agents also contain solvents, and will consequently be able to give positive hydrocarbon test after the cleaning. ence the tanks must be washed thoroughly with water after use of such cleaning agents. Some residues have very high melting points, which makes them difficult to emulsify. To clean such residues it Marstal Navigationsskole April 14

144 144 re 4: re 5: may be necessary to use a solvent. Frequently used solvents are toluene or white spirit. Both may be applied by spraying or by the lift method (see below). Some residues are persistent enough to make it necessary to heat the solvent, and care should be taken to choose a solvent with a sufficiently high boiling point. Whenever possible the cleaning procedures adopted should not involve personnel entering a non-gas free tank. If however it is necessary to enter the tank, all precautions should be taken to protect the personnel involved from the health hazard of the cleaning solvent and a flammable solvent should only be used for spot-cleaning and never for spraying in a non-inerted tank. hemical reactions are rarely used for tank cleaning purposes, but may be the only alternative if some unwanted reaction during the voyage or during the initial cleaning has left an insoluble residue on the tank walls. Furthermore chemical reaction may be used to remove rust (iron oxide) from the coating and the piping. When undertaking an operation involving chemical reactions, advice should be sought from competent companies. Another way to dissolve solid residues is by steaming or even by steaming with a solvent (for example toluene) or an alkaline cleaning agent. Steaming with solvents like toluene should only be carried out in inerted tanks due to the risk of ignition by static electricity. All the above-mentioned cleaning agents may be applied in a number of ways, which in brief can be described as follows: The injection method This method is practised by injecting the cleaning agent (caustic, detergent or solvent) directly into the tank cleaning line either on deck or in the pump room. There are several methods to use by injection with chemicals during tank cleaning, into the mechanical tank wash system but the method preferred for tank cleaning at sea is: Inject the chemical directly into the tank-wash line on deck. The chemical is injected from a 200 litre drum directly into the tank-wash line on deck by means of an air operated pump on the drum, a small needle valve and a short hose, connected to a spare tank-wash hose valve. The main benefit of this method is that the injection and correct dosage of chemical can be regulated and controlled at any place on deck, close to the tanks being washed. The recirculation method In general this method of tank cleaning with a chemical solution is highly effective. One of the vessel's tanks is used to mix a suitable solution of the cleaning agent (for example a 0.2 % detergent solution). The mixture is pumped through the cleaning line and the cleaning machines and is stripped back to same tank. To work properly this method demands a good preliminary cleaning as otherwise the cleaning mixture will quickly Marstal Navigationsskole April 14

145 145 become inefficient. A great advantage of the re-circulation method is that both heat and chemicals are recovered and used over and over again until one or more tanks are completely cleaned. The effect of cleanliness may improve if a suitable filtering system can be used between the pump and the cleaning machines. The most common system is to insert a strainer into the X-tree when connection is made on the pump stack. Remember: Re-circulation is only permitted between inerted tanks or gas-free tanks. Recirculation with chlorinated solvents The preferred products purchased/supplied should be non-contaminated Trichloroethylene and or Perchloroethylene. If the moisture content is not more than a few hundred ppm, the chlorinated solvent should be acceptable for most re-circulation operations. A larger quantity (10 to 15 tons) of Methylene hloride (ME) is usually requested for cleaning after discharging of isocyanates like TDI and MDI, but only when compatible with the coating. Equipment for recirculation and must be clean and chemical resistant to chlorinated solvents. Furthermore, chlorinated compounds tend to hydrolyse in the presence of water and form organic or mineral acid. Bleach Bleach is also known as lorox and Dixichlor. The chemical name is Sodium ypochlorite Solution (11 13%), which is a strong oxidizer. The name Bleach is used throughout this procedure. Precaution: The product is very aggressive p 14, - in particular to stainless steel and the aggressiveness increase with raised temperatures. Any bleach solution must not be allowed to dry on any tank lining or stored in cargo tanks as cleaning solution or slops. Bleach solution should mainly be used in coated tanks and when diluted to maximum 1 % strength. Diluted bleach is used for following purposes: Removal of odour, if present after normal tank cleaning. Removal of colour, if present after normal tank cleaning. (olour may be present after last cargoes having strong colour which is also the case after dyed gasoline). Improving the Permanganate Time Test, if low after normal tank cleaning. (Low PTT is often the result of a reducer remaining on the tank surface, which originates from an inhibitor or the cargo itself). The bleach is known to be contrary to a reducer, which is an oxidation agent. Procedure: After any seawater washing, ensure to thoroughly fresh water rinse the tank before preparing the bleach solution. Prepare the tank for re-circulation. Add fresh water into the tank enough for the recirculation and add maximum 1 % of bleach into the tank by the drop line. Secure the tank and start re-circulation immediately. Apply the tank heating system and bring the temperature up to maximum 50. On completion close the tank-heating system. If a second tank needs the same cleaning method, it should be prepared for recirculation prior to transferring the used bleach solution. Marstal Navigationsskole April 14

146 146 During re-circulation temperature should not exceed 50 due to the solution s aggressiveness. and spraying is not recommended. Immediately after re-circulation, rinse the tank with warm sea- or fresh water for three machine cycles. After the end of rinsing, take a sample from the discharge line and inspect it for traces of remaining bleach, odour, foam, p-value etc. If the bleach solution is still present, the rinsing should continue until outcome rinsing water is free of bleach and p-value is the same as the incoming rinsing water. On completion of rinsing, continue with chloride free sistilled water in order to remove the salt/chloride because if bleach is still present in the coating, it will affect the chloride test. Warning. If bleach solution is not washed off immediately after re-circulation or if it is stored in cargo tanks, in particular stainless steel tanks, corrosion and or coating damage can be expected very soon. The lift method In some situations it may be convenient or necessary to apply a solvent or cleaning oil to the tank walls. This is done by pouring the solvent into a tank and then slowly lifting the solvent by pumping water in below it. The lift should not exceed about 1 metre per hour, and thus the method is very slow. When the tank is full the water level is lowered again by pumping the water to a slop tank. When the tank is almost empty the rest of the cleaning agent is pumped into the next tank and the procedure starts all over again. Toluene has often been used as the medium. Toluene is a highly static electricity generator, so extreme care must be taken with the bonding of all equipment used for the operation. One of the leading tank cleaning laboratories in the world, Dr. Verwey, does not recommend Toluene Floating. and spray method The method is undertaken by spraying a cleaning agent directly onto the surfaces of the tank. After a certain time, during which the cleaning agent works on the residues, the tank is water washed in a normal pattern. This method is very efficient and the consumption of cleaning agent is reasonably low, but it should be borne in mind that it Marstal Navigationsskole April 14

147 147 is very important to protect the crew involved in the operation, as many cleaning agents are rather dangerous to personnel. Also, this method should never be used with a flammable cleaning agent due to the risk of an electrostatic ignition. Type of spray equipment to be employed varies from simple hand operated sprayers to compressed air driven pumps, pressure tanks, all connected via sufficient length of chemical resistant hose to a suitable spray gun. For manual spraying it is highly recommended to use airless type spray guns, thus spraying tank-cleaning solvents under pressure without air-atomisation. All personnel who enter the tank during inspection, control, repair, maintenance etc., must wear soft-soled shoes. This is of special importance for epoxy-coated tanks, which have been exposed to chemicals, softening the coating. Atomisation method The principle is the same as mentioned for the hand spray method, but instead of sending men into the tanks to apply the cleaning agent, a lance-like apparatus with fine nozzles is introduced into the tank. The cleaning agent is pumped through the nozzles and after some time the tanks are water washed. As this method almost invariably will generate large electrostatic potentials, it should only be used in inerted tanks or in gas-free tanks with a non-flammable cleaning agent. Steaming method This procedure is mostly done after tank cleaning, and before loading of chemicals. To make the tanks free of hydrocarbons, chlorides, also for a Permanganate Time Test. For this matter we have a choice of several types of chemicals, like aromatics, alcohols, ketones and products like perchloroethylene or trichloroethylene. It is a matter of fact that the choice of chemical for steaming complies with instructions of the coating supplier. When steaming the tank with chemicals one have to consider about the lower flammable limit (LFL or LEL). Steaming with hemicals alculation of volume percentage: The volume of vapour (gas) is equal to the number of mole multiplied by 24 litres, when the temperature is 20. The number of mole is found as the amount of chemical in kilograms divided by the mole mass. Example: Steaming with 4 litres of toluene 7 8. Density 0.86 kg/l, mole weight 92 g/mole, flammable range: LFL = 1.2 UFL =7.0 volume % 4 litre 860 g/l 24 l/mole 92 g/mole 897litre In a 1000m 3 tank, 897 litre of vapour gives a concentration of 0.09 volume %. The volume of 1 mole at 60, which easily might be the tank temperature during steaming, is 27 litres instead of 24 litres. Then the volume of 4 litre toluene as vapour will be 1020 litre, and the concentration in a 1000 m 3 tank will then be 0.10 volume %. Marstal Navigationsskole April 14

148 148 alculation to stay below Lower Flammable Limit (LFL) Steaming with methanol in a 1000 m 3 cargo 60 : 3 O, density 790 g/l, Mole weight 32 g/mole. Flammable range: LFL = 5.5 UFL =36.5 volume % 55,000l 5.5 vol% of the cargo tank capacity is 55,000 l vapour equal to 2037mole. 27l / mole The mass of 2037mole is 2037mole 32 g/mole = kg of methanol = litres. Then the Lower Flammable limit is reached! Special considerations for Stainless Steel Tanks made of stainless steel cannot always be cleaned in the same way as coated tanks. The primary resistance of stainless steel is a thin layer of chromic oxide which is created on the surface of the steel. This layer is resistant to most chemicals, but rather sensitive to substances containing chloride such as sea water. Stainless tanks should thus preferably be washed with fresh water only, but if it for some reason is necessary to use sea water, the tanks should be flushed with fresh water without delay. Fresh Water Flushing For all kinds of tanks it may be necessary to undertake a final rinsing with fresh or even destilled water to remove any chlorine residues or residues from cleaning agents, which may react with the next cargo. Ventilation and Drying Any tank cleaning operation is concluded by ventilating and drying the tanks with air. Drying of tanks The drying of the tanks is in fact done in the way that the air blown into the tank picks up the humidity of the tank atmosphere, and thereby removing the water from the tank when the air again leaves the tank. owever it is important to remember a few fundamental principles of how air can accumulate/contain humidity. The relation between the temperature of the air and the water content in g/m 3 is so, that the air is able to contain a higher amount of humidity at a higher temperature as it is seen from the curves: Marstal Navigationsskole April 14

149 149 On the diagram is given the absolute humidity in g/m 3 on the left axis, and the relative humidity in % on the right axis as a function of the temperature. When the air reaches a relative humidity of 100% the air is saturated and then no longer capable to take up more humidity. An example will show that only about 1,5 grams of water vapour can be removed per m 3 of supplied air if the air blown in has a temperature of 20 and a relative humidity of 90%, which is not unusual when at sea. One also has to be aware that there is no reason in trying to dry tanks if the empty tanks are surrounded by cold ballast tanks where the steel temperature is below the dew point of the air blown in. From the curves can be read as an example that a 20 warm air with a relative humidity of 90% will start to condense if the temperature of the air falls to below about 18. So therefore it can be recommended that the dew point of the air is determined and compared with the steel temperature of the tank if in doubt whether it is worth while to start drying tanks now or wait until the relative humidity is lower. In some ships it is possible to dry the air before it is blown into the tanks. This can be done by means of for example a Münters Dryer or by blowing the air through receptacles (cylinders) filled with a moisture absorbing substance, which later can be regenerated. Using those methods the dew point of the air can be significantly lowered, and the air will therefore be able to remove considerably larger quantities of water per m 3 air and furthermore it will be possible to dry even very cold steel bulkheads. If the tanks are equipped with heating coils or if the ship is equipped with an air heater then it will be possible to heat up the tanks during the drying, and it will be seen from the curve above that a raise in temperature from for instance 20 to 25 will make it possible to remove about 8 grams of water per m 3 in stead of only 1,5 grams per m 3. The heating will of cause also result in a higher steel-temperature, so condensation will be less probable; but in practice it is often seen that it is difficult to catch the under side of the deck, which results in condensation under the deck and rain in the tanks. Marstal Navigationsskole April 14

150 150 Inspection hemical cargoes will mostly demand very clean tanks. Normally the shipper will appoint a surveyor to inspect the ship's tanks and a number of independent survey companies undertake such commissions. The vessel should always ensure proof of any inspection carried out. Marstal Navigationsskole April 14

151 151 Wall Wash Tests When the surveyor inspects the tanks, he often carries out different tests to ensure the cleanliness of the tank bulkheads and horizontal surfaces. Such tests could be test: 1. olour test 2. ydrocarbon test 3. hloride test 4. Acid wash colour test 5. Permanganate time test 6. Test for p value etc. Some of these tests can be made by the crew itself, and if sufficient time is at hand, tests should be made before arrival to ensure that any residues and traced are removed, thus avoiding the rejection of the tanks. Some of the tests are easy to do, for instance p test, hydrocarbon test and chloride test. Other tests require more attention and experience and some tests even need a kind of laboratory on board the ship. Many operators have equipped their tankers with a Wall Wash Test Kit e.g. from the well-known chemical laboratory Dr. Verwey in Rotterdam. When that is the case, it is important carefully to read the instructions supplied by the supplier of the test kit. Evaluation of Wall Washing and Testing It is important to know that many factors have an influence on the test result. Also factors that are not always obvious. ere follows some reflections on what to have in mind when evaluating the result of wall wash tests: Wall Wash Sample Possible sources affecting the sample: Test Result Possible sources affecting the test: onsequence of this: WALL WAS MEDIUM W/WAS AND TEST MEDIUM YDROARBONS? EQUIPMENT LEANLINESS DI-WATER (TEST WATER) PTT? WALL WAS METOD LEANLINESS OF EQUIPMENT LORIDES? WET/WARM BULKEAD POOR QUALITY EQUIPMENT ODOUR? SOFT OATING SORTAGE OF EQUIPMENT OLOUR? PREVIOUS ARGOES POOR LAB. ONDITION APPEARANE? WASING WATER (PURITY) LAK OF EXPERIENE SUSPENDABLES? SEA PLANKTON RUSING TEST WORK UV? LEANING EMIALS (SOAP) FILTERING (PURITY) NVM (NON VOLATILE MATERIAL) LORIDES IN FW STEAM OSES (LEANLINESS) LORIDES IN STEAM ARGO/FUEL IN STEAM TEMPERATURE (AURAY) LIGT QUALITY OF KMnO 4 RYSTAL QUALITY OF KMnO 4 SOLUTION BOILER EMIALS QUALITY OF AgNO 3 VENTILATION METODS STANDARDS (MISSING) TANK VENTILATORS (OIL) POLLUTED AIR (IN PORT) SUSPENDABLES BALLASTING DETETING METODS MARKING & NOTATIONS Marstal Navigationsskole April 14

152 152 Products Products can be divided in different groups for cleaning purposes like: Group 1 Water soluble Group 2 Light ydrocarbons Group 3 ydrocarbon test problems Group 4 Permanganate or activity problems Group 5 ydrocarbon test, permanganate, and cleaning problems Group 6 Leaded or dyed products Group 1: Group 2: Group 3: Acid Toluene Naphta Alkohols Benzene Alkyl benzene Amines Trichloroethylene Diesel oil austic umene Dioctyl Phthalate Esters yclohexane Gasoline (unleaded/-dyed) Glycols Xylene Gas oil Ketones exane Kerosene Ethylene dichloride Lubricating oil Perchloroethylene Propylene tetramer Group 4: Group 5: Group 6: Styrene monomer ottonseed oil Gasoline (leaded or dyed) Vinyl acetate monomer Soybean oil Dyed products Acrylates Fish oil Methyl acrylates oconut oil Isoprene Fatty Acids Acrylonitrile Molasses Toluene diisocyanate Palm oil Phenol Safflower oil resols Linseed oil Furfural Raffinate Marstal Navigationsskole April 14

153 153 Pollution regulations Introduction The international community has become seriously concerned about ship-generated marine pollution in recent years. More than 80 international conventions and related instruments address the problem. Among these MARPOL is considered as the most important. MARPOL, which deals with all forms of marine pollution except the disposal of land-generated waste into the sea by dumping, was born as a result of an international onference. In 1969, the IMO Assembly inspired partly by the Torrey anyon disaster of two years before decided to convene an international conference to adopt a completely new convention. The conference met in London in 1973 and IMO adopted the International onvention for the Prevention of Pollution from Ships, This was modified by a protocol in 1978 and is now usually known as MARPOL 73/78. The convention finally entered into force in October 1983 ten years after the first conference was held. Marpol 73/78 Marpol 73/78 has three Protocols dealing respectively with Reports on Incidents involving armful Substances, on Arbitration and The Protocol of 1997 (Annex VI) and six Annexes which contain regulations for the prevention of the various forms of pollution: Annex I Pollution by Oil Annex II Pollution by Noxious Liquid Substances carried in bulk Annex III Pollution by armful Substances arried By Sea In Packaged Form Annex IV Pollution by Sewage from Ships Annex V Pollution by Garbage from Ships Annex VI Air Pollution from Ships Marstal Navigationsskole April 14

154 154 The relevant Annexes "Discharge", As chemical tankers transport both oil products and noxious liquid substances it is relevant to deal with both Annex I and Annex II. In the Definitions section in MARPOL it is worth noting that harmful substance includes any substance discharged into the sea which is liable to: create hazards to human health, harm living resources and marine life, damage amenities or interfere with other legitimate uses of the sea. in relation to harmful substances or effluents containing such substances, means any release howsoever caused from a ship and includes any escape, disposal, spilling, leaking, pumping, emitting or emptying. "Discharge" does not include: dumping within the meaning of the London onvention, or release of harmful substances directly arising from offshore exploration, exploitation and associated processing of sea-bed mineral resources; or release of harmful substances for purposes of legitimate scientific research into pollution abatement or control. "Ship" means a vessel of any type whatsoever operating in the marine environment and includes hydrofoil boats, air-cushion vehicles, submersibles, floating craft and fixed or floating platforms. MARPOL Annex I, Regulations for the Prevention of Pollution by Oil In MARPOL oil is defined as being any kind of mineral oil and mixtures thereof, including crude oil, natural gas condensate, oil sludge and oily residues, fuel oils and all other refined oil products except petrochemicals which are classified according to the regulations concerning noxious liquid substances in bulk. A List of oils is found in Appendix I to Annex I: Marstal Navigationsskole April 14

155 155 Appendix I List of oils Asphalt solutions Blending stocks Roofers flux Straight run residue Oils larified rude oil Mixtures containing crude oil Diesel oil Fuel oil no. 4 Fuel oil no. 5 Fuel oil no. 6 Residual fuel oil Road oil Transformer oil Aromatic oil (excluding vegetable oil) Lubricating oils and blending stocks Mineral oil Motor oil Penetrating oil Spindle oil Turbine oil Distillates Straight run Flashed feed stocks Gas oil racked Gasoline blending stocks Alkylates-fuel Reformates Polymer-fuel Gasolines asinghead (natural) Automotive Aviation Straight run Fuel oil no. 1 (kerosene) Fuel oil no. 1-D Fuel oil no. 2 Fuel oil no. 2-D Jet fuels JP-1 (kerosene) JP-3 JP-4 JP-5 (kerosene, heavy) Turbo fuel Kerosene Mineral spirit Naphtha Solvent Petroleum eartcut distillate oil This list of oils shall not necessarily be considered as comprehensive. Marstal Navigationsskole April 14

156 156 Annex I applies to all ships to which MARPOL 73/78 applies which means virtually all ships except warships or similar ships owned or operated by a State. The discharge of oil or oily water into the sea is prohibited in some areas and severely restricted in others. Ships are required to meet certain equipment and constructional standards and to maintain an Oil Record Book. With the exception of small ships, a survey is required and, for ships trading internationally, certification in a prescribed form is necessary. Ports are required to provide adequate reception facilities for oily mixtures and residues to meet the needs of ships using the ports. The requirements for the control of operational discharges of oil are given in regulations 15 (from machinery spaces) and 34 (cargo area from oil tankers) of Annex I. The rules for discharge of oily water from tankers are briefly: Within 50 nautical miles from nearest land and in "Special Areas" (which are Mediterranean Sea area, the Baltic Sea area, the Black Sea area, the Red Sea area, the "Gulfs area", the Gulf of Aden area, the Northwest European area, the Oman area of the Arabian Sea, the Southern South Africa Sea Area and the Antarctic area) discharge of oily water from the cargo area is prohibited. Discharge outside these areas is allowed provided that a) the tanker is proceeding en route, b) the instantaneous rate of discharge of oil content does not exceed 30 litres per nautical mile, c) the total quantity of oil discharged into the sea does not exceed 1/ of the total quantity of the particular cargo of which the residue formed a part (for ships built according to old rules 1/15.000), d) the tanker has in operation an oil discharge monitoring and control system and an approved slop tank arrangement. The provision of above shall not apply to the discharge of clean or segregated ballast. Marstal Navigationsskole April 14

157 157 Special Area Annex I and Also Waters South of 60º S are MARPOL Annex I Special Areas Rules for discharge of oily water from machinery spaces are given in regulation 15 of Annex I. They apply to tankers as well as other ships over 400 GT. Discharge of oil or oily water is prohibited unless following rules are observed: Discharge from cargo area, oil tanker: 1. Transfer the oily waste into a slop tank. 2. Ship must be outside special Area and >50 nautical miles from nearest land 3. Proceeding en route 4. An Oil Discharge Monitoring and control System (ODME) must ensure that: 5. Instantaneous discharge rate <30litres per nautical mile, and 6. Total quantity of oil discharged does not exceed 1/30000 of previous cargo Discharge of oil from machinery spaces of all ships: 1. Any discharge in Antarctic area is prohibited 2. Proceeding en route 3. Oily mixture is processed through an oil filtering equipment 4. No more than 15 parts per million of oil in the effluent 5. Automatic stopping devise when 15 ppm is exceeded 6. Alarm when 15 ppm is exceeded 7. Oily mixture does not originate from cargo area of oil tankers Marstal Navigationsskole April 14

158 158 MARPOL Annex II, Regulations for the ontrol of Pollution by Noxious Liquid Substances in Bulk Liquid substances are defined as being substances having a vapour pressure not above 0.28 MPa absolute (2.8 bar) at 37.8 (100 F), i.e. substances, which may be transported in a liquid state at ambient temperature and pressure. Liquid substances, which are transported in bulk, must be classified according to the criteria laid out in MARPOL's Annex II, and substances, which are judged as harmful may only be discharged according to particular criteria. The regulations controlling the discharge of harmful liquid substances are explained on the following pages. Substances, which have not been categorized, have to be provisionally assessed by the authorities before transportation. The structure of Annex II The regulations ategory X: Annex II consists of 18 regulations giving detailed requirements for discharge criteria and measures for the control of pollution by Noxious Liquid Substances (NLS) carried in Bulk. The principles on which the operational aspects of MARPOL 73/78 are based are: stripping of cargo tanks after unloading; the ship s speed during discharge of tank washings; the minimum distance from the nearest land during discharge; the minimum depth of water during discharge; the need to effect the discharge below the waterline. Furthermore Annex II contains seven appendixes giving guidelines for the categorization of noxious liquid substances, a recommended layout for the argo Record Book and the form of the so-called NLS ertificate. Annex II also contains an appendix giving the standard format for the Procedures and Arrangement Manual, (P&A Manual). Appendix 5 to MARPOL Annex II is: Assessment of residue quantities in cargo tanks, pumps and associated piping. Then appendix 6 explains the prewash procedures and finally appendix 7 deals with ventilation procedures when removing cargo residues by ventilation. Basically Annex II applies to all ships carrying noxious liquid substances in bulk where a noxious liquid substance is defined as any substance falling into pollution category X, Y, or Z. The pollution categories are explained as: Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a major hazard to either marine Marstal Navigationsskole April 14

159 159. ategoryy: ategory Z: resources or human health and, therefore, justify the prohibition of the discharge into the marine environment. Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a hazard to either marine resources or human health or cause harm to amenities or other legitimate uses of the sea and therefore justify a limitation on the quality and quantity of the discharge into the marine environment. Noxious Liquid Substances which, if discharged into the sea from tank cleaning or deballasting operations, are deemed to present a minor hazard to either marine resources or human health and therefore justify less stringent restrictions on the quality and quantity of the discharge into the marine environment. List of noxious liquid substances carried in bulk List of other liquid substances The discharge of tank washing containing ategory X, Y or Z: Noxious liquid substances carried in bulk and which are presently categorized as ategory X, Y or Z and subject to the provisions of Annex II, are so indicated in the pollution category column of chapters 17 or 18 of the International Bulk hemical ode, - the IB - code. Liquid substances carried in bulk which are identified as falling outside the ategories X, Y or Z and not subject to the provisions of Annex II are indicated as "OS", (short for Other Substances ) in the pollution category column of chapter 18 of the International Bulk hemical ode (IB code). It is in this connection worth noting that the discharge of bilge or ballast water or other residues or mixtures containing only substances indicated as OS in Annex II shall not be subject to any requirement of this Annex. The discharge into the sea of clean ballast or segregated ballast as well shall not be subject to any requirement of this Annex. For all three pollution categories discharge into the sea is prohibited unless the following three conditions are observed: the ship is proceeding en route 1 at a speed of at least 7 knots in the case of self-propelled ships or at least 4 knots in the case of ships which are not self-propelled; 1 En route means that the ship is under way at sea on a course or courses, including deviation from the shortest direct route, which as far as practicable for navigational purposes, will cause any discharge to be spread over as great an area of the sea as is reasonable and practicable. Marstal Navigationsskole April 14

160 160 the discharge is made below the waterline through the underwater discharge outlet(s) not exceeding the maximum rate for which the underwater discharge outlet(s) is (are) designed; and the discharge is made at a distance of not less than 12 nautical miles from the nearest land in a depth of water of not less than 25 metres. 2 Ventilation of cargo residues Approved ventilation procedures may be used to remove cargo residues from the tanks. The following is an extract from MARPOL Annex II Appendix 7, Ventilation procedures : Ventilation procedures 1. argo residues of substances with a vapour pressure greater than 5 kpa (50 mbar) at 20 may be removed from a cargo tank by ventilation. 2. Before residues of Noxious Liquid Substances are ventilated from a tank the safety hazards relating to cargo flammability and toxicity shall be considered. With regard to safety aspects, the operational requirements for openings in cargo tanks in SOLAS 74, as amended, the International Bulk hemical ode, the Bulk hemical ode, and the ventilation procedures in the International hamber of Shipping (IS) Tanker Safety Guide (hemicals) should be consulted. 3. Port authorities may also have regulations on cargo tank ventilation. 4. The procedures for ventilation of cargo residues from a tank are as follows: 2 Depth of water means the charted depth. Marstal Navigationsskole April 14

161 161.1 the pipelines should be drained and further cleared of liquid by means of ventilation equipment;.2 the list and trim should be adjusted to the minimum levels possible so that evaporation of residues in the tank is enhanced;.3 ventilation equipment producing an airjet which can reach the tank bottom shall be used;.4 ventilation equipment should be placed in the tank opening closest to the tank sump or suction point;.5 ventilation equipment should, when practicable, be positioned so that the airjet is directed at the tank sump or suction point and impingement of the airjet on tank structural members is to be avoided as much as possible; and.6 ventilation shall continue until no visible remains of liquid can be observed in the tank. This shall be verified by a visual examination or an equivalent method. Any water subsequently introduced into the tank shall be regarded as clean and shall not be subject to the discharge requirements given in MARPOL Annex II. Efficient stripping ontrary to the discharge of water containing oil residues from oil cargoes, where the oil content can be detected by an oil content monitor, it is not possible to construct a detector which can detect all residues from chemicals. Therefore, in order to ensure that only a minimum of noxious liquid substances are discharged into the sea during the disposal of tank cleaning water, MAROL Annex II requires that the ship must be constructed with so-called efficient stripping. The construction requirements differ in three levels : 1. Ships constructed before 1 July (Also called B-ships ), 2. ships constructed on or after 1 July 1986 but before 1 January 2007 ( existing IB-ships ), and 3. ships constructed on or after 1 January 2007 ( new ships ). ad1) Every ship constructed before 1 July 1986 shall be provided with a pumping and piping arrangement to ensure that each tank certified for the carriage of substances in ategory X or Y does not retain a quantity of residue in excess of 300 litres in the tank Marstal Navigationsskole April 14

162 162 Important! and its associated piping and that each tank certified for the carriage of substances in ategory Z does not retain a quantity of residue in excess of 900 litres in the tank and its associated piping. A performance test shall be carried out in accordance with appendix 5 of Annex II. ad 2) Every ship constructed on or after 1 July 1986 but before 1 January 2007 shall be provided with a pumping and piping arrangement to ensure that each tank certified for the carriage of substances in ategory X or Y does not retain a quantity of residue in excess of 100 litres in the tank and its associated piping and that each tank certified for the carriage of substances in ategory Z does not retain a quantity of residue in excess of 300 litres in the tank and its associated piping. A performance test shall be carried out in accordance with appendix 5 of Annex II. ad 3) Every ship constructed on or after 1 January 2007 shall be provided with a pumping and piping arrangement to ensure that each tank certified for the carriage of substances in ategory X, Y or Z does not retain a quantity of residue in excess of 75 litres in the tank and its associated piping. A performance test shall be carried out in accordance with appendix 5 of Annex II. The stripping test shall be performed by using water as the stripping media. For B-ships and existing IB-ships a tolerance of 50 litres per tank is acceptable. For example, an existing IBship can be accepted even if the stripping test shows up to 150 litres. Verifying the efficience of a stripping test on board a newbuilding in Rumania Marstal Navigationsskole April 14

163 163 Reception facilities Ports must have adequate reception facilities for any tank washings or residues that must be discharged in compliance with Annex II and terminals must have suitable arrangements to facilitate the stripping of ship s cargo tanks. It is important to note that cargo hoses and piping systems of the terminal, containing noxious liquid substances received from ships unloading these substances at the terminal, shall not be drained back to the ship. Remember: argo hoses and piping systems of the terminal, containing Noxious Liquid Substances received from ships unloading these substances at the terminal, shall not be drained back to the ship. Marstal Navigationsskole April 14

164 164 Measures of control Prewash and endorsement in argo Record Book by MARPOL Annex II surveyor MARPOL Annex II Regulation 16 states that the government of each Party to the convention shall appoint or authorize surveyors who shall execute control of for instance the unloading and prewash in accordance with control procedures developed by IMO and adopted by Resolution A.787(19) and amended by A.882(21). The surveyors shall as a minimum endorse in the argo Record Book entries of prewash operations after category X products. If the ship has been given any exemptions from mandatory prewash, such exemptions shall also be endorsed by the surveyor. At the request of the ship's master, the Government of the receiving party may exempt the ship from the requirements of prewash where it is satisfied that: (i) the unloaded tank is to be reloaded with the same substance or another substance compatible with the previous one and that the tank will not be washed or ballasted prior to loading, or (ii) the unloaded tank is neither washed nor ballasted at sea. The prewash shall be carried out at another port provided that it has been confirmed in writing that a reception facility at that port is available and is adequate for such a purpose, or (iii) the cargo residues will be removed by ventilation. Special cases where prewash is required If the unloading of category Y or Z substances is not carried out in accordance with the approved pumping conditions, which is the case when the efficient stripping system has not been in use, or if the substance unloaded has been identified as a solidifying or high viscosity substance then the tanks shall be prewashed before the ship leaves the port of unloading. It is possible to obtain an exemption from the prewash in accordance with the conditions given above. In MARPOL Annex II regulation 1 solidifying substance and high-viscosity substance is defined. A noxious liquid substance shall be regarded as a Solidifying substance: 1. if the melting point is lower than 15 and the cargo temperature at the time of unloading is less than 5 above its melting point; or 2. if the melting point is equal to or greater than 15 and the cargo temperature at the time of unloading is less than 10 above its melting point. Marstal Navigationsskole April 14

165 165 Benzene can be used as an example to illustrate the problem. Benzene has a melting point of 6 and therefore the temperature at the time of unloading must be at least 11 if benzene shall not be considered as solidifying and for that reason require a prewash. A noxious liquid substance shall be regarded as a ighviscosity substance: in the case of category X and Y substance with a viscosity equal to or greater than 50 mpa s at the unloading temperature. It is a requirement of chapter 16 in the IB-code that the viscosity at 20 and the melting point should be stated on the shipping documents if it is relevant. If the viscosity at 20 exceeds 50 mpa s it should be stated at which temperature the viscosity will be down to 50 mpa s. Removal of solidified palm stearine from cargo pipes the hard way Marstal Navigationsskole April 14

166 166 More about viscosity: As many category Y - substances might require prewash of cargo tanks after unloading because of the cargo being igh viscosity at the unloading temperature, it will be appropriate to refresh the connection between different units of viscosity: MARPOL Annex II defines igh Viscosity in Regulation 1.17as: 17. Viscosity 17.1 igh-viscosity Substance means a noxious liquid substance in ategory X or Y with a viscosity equal to or greater than 50 mpa.s at the unloading temperature Low-Viscosity Substance means a noxious liquid substance, which is not a igh-viscosity Substance. When there is a chance that a substance might become igh-viscosity, there will be a reference in the IB code chapter 17 column o to IB code : Where column o in the table of chapter 17 refers to this paragraph, the cargo s viscosity at 20 shall be specified on a shipping document, and if the cargo s viscosity exceeds 50 mpa.s at 20, the temperature at which the cargo has a viscosity of 50 mpa.s shall be specified in the shipping document. ow to proceed: When the viscosity is indicated in the shipping document in the unit milli Pascal multiplied by second or mpa s, we are on safe ground! Dynamic Viscosity mpa s is equal to another expression for the dynamic viscosity, namely cpoise or centipoise or cp. (The SI unit for dynamic viscosity is N s/m 2 ). Kinematic Viscosity Often the viscosity is indicated in the shipping document in the unit centistokes or cst. (The SI unit for kinematic viscosity is m 2 /s. Important: 1 mm 2 /s is equal to 1 cst. onversion to mpa s 1. mpa s = cpoise 2. mpa s = viscosity given in centistokes multiplied by the cargo density in g/cm 3. (The viscosity and density given at the same temperature) Other useful relations: 1 cst = 10-6 m 2 /s = 1 mm 2 /s Viscosity and reference temperatures The viscosity of a fluid is highly temperature dependent and for either dynamic or kinematic viscosity to be meaningful, the reference temperature must be quoted! Marstal Navigationsskole April 14

167 167 Viscosity and handling temperature of selected vegoils The revised MARPOL Annex II requires Prewash after unloading of substances of pollution category Y when the substances are solidifying or high viscosity substances. A substance is a high viscosity substance when the viscosity at the unloading temperature is more than 50 mpa s. The list below shows the carriage temperature and unloading temperature together with viscosity for selected vegoils. (Guidance only) SUBSTANE NORMAL ARRIAGE TEMP. NORMAL DISARGE TEMP. VISOSITY AT 20 TEMP. FOR VISOSITY = 50 mpa s astor oil oconut Oil EATING INST. orn Oil Amb @ ottonseed Oil Amb.-amb Fish Oil Groundnut Oil Amb.-amb E Rapeseed Oil Amb.-amb Lard Solid 35 Linseed Oil Amb.-amb Olive Oil Amb.-amb Palm Acid Oil Solid Palm Fatty Acid Distillate Solid Palm Kernel Oil Semi- Solid 28 Palm Oil Semi- Solid 44 Palm Olein Semi- Solid 29 Palm Stearin Solid 54 Rapeseed Oil/anola Oil Amb.-amb Soyabean Oil Amb.-amb Sunflower Oil Amb.-amb Tallow Solid 45 Tung Oil Amb.-amb Marstal Navigationsskole April 14

168 168 Nomogram for temperature correction of viscosity Vegoils are listed in IB ode chapter 17 with pollution category Y. If the product s viscosity at unloading temperature exceeds 50 mpa s ( = 50 cpoise) the tank has to be prewashed. As viscosity depends on temperature the nomogram below can be used as a tool to determine the temperature at which the cargo shall be unloaded in order to lower the viscosity below 50 mpa s and thereby avoid a prewash. Remember: always obtain permission before heating the cargo! NOMOGRAM FOR TEMPERATURE ORRETION OF VISOSITY To use the nomogram connect known values of temperature and viscosity with a straight line (e.g. 750 cp at 20 : line (1)). The intersection of this line with the reference line gives a reference point. Draw a line from the known temperature through this reference point to intersect the viscosity scale. This gives the viscosity at this temperature (e.g. line (2): at 80 the viscosity is found to be 29 cp). *) For conversion in SI Units: 1 centipoise (cp) = 1 millipascal second (mpa s) Marstal Navigationsskole April 14

169 169 argo Record Book Every ship to which Annex II applies shall be provided with a argo Record Book, whether as part of the ship's official log-book or otherwise, in the form specified in appendix IV to Annex II. The argo Record Book shall be completed, on a tank-totank basis, and shall cover operations such as loading, unloading and internal transfer of cargo; ballasting, discharge of ballast and cleaning of cargo tanks; disposal of residues to reception facilities, discharge into the sea or removal of residues by ventilation. Each operation shall be promptly recorded in the argo Record Book so that all the entries in the book appropriate to that operation are completed. Each entry shall be signed by the officer or officers in charge of the operation concerned and each page shall be signed by the master of the ship. The entries in the argo Record Book shall at least be in English, French or Spanish. The argo Record Book shall be kept in such a place as to be readily available for inspection and it shall be retained for a period of three years after the last entry has been made. Survey and certification Surveys are required for all ships to cover Annex II requirements; the condition of the ship and its equipment is to be maintained and may not be changed without prior sanction of the marine administration. An International Pollution Prevention ertificate for the arriage of Noxious Liquid Substances (NLS ertificate) is required for ships in international trade. hemical tankers which have been surveyed and certified by the marine administration in accordance with the IB ode or the B ode should be accepted as complying with the requirements and do not require a NLS ertificate or an additional survey. Such a ship must have a ertificate of Fitness as required by the IB code. Port State control on operational requirements A ship when in a port of another Party to MARPOL is subject to inspection by officers duly authorized by such Party concerning operational requirements under Annex II, where there are clear grounds for believing that the master or crew are not familiar with essential shipboard procedures relating to the prevention of pollution by noxious liquid substances. Marstal Navigationsskole April 14

170 170 Resolution A.787(19) Procedures for Port State ontrol as amended by resolution A.882(21) says that if the deficiencies found in a ship are serious the Port State ontrol Officer shall take such steps as will ensure that the ship shall not sail until the situation has been brought to order in accordance with the requirements of Annex II. The Guidelines to the resolution shows a list of deficiencies which are considered to be of such a serious nature that they may warrant the detention of the ship involved. This list is not considered exhaustive but is intended to give examples of relevant items. The following is an extract of the list: Areas under the MARPOL onvention, Annex II 1) Absence of P & A Manual. 2) argo is not categorized. 3) No argo Record Book available. 4) Transport of oil-like substances without satisfying the requirements. 5) Unauthorized discharge bypass fitted. Procedures and Arrangement Manual (P&Amanual) Any ship, which is certified to carry substances of category X, Y or Z shall have on board a Manual approved by the Administration (Maritime Administration or classification society). The manual must carefully describe all procedures to be followed in connection with cargo-handling, tank cleaning, discharge into the sea, ventilation and not least prewash. Obviously these procedures must be in full accordance with the provisions of Annex II. Furthermore the P&A-manual must contain a detailed description of the cargo handling equipment such as description of cargo pumping and piping arrangements and stripping system; description of underwater discharge outlet for effluents containing noxious liquid substances; type of tank washing machines with capacities and pressure rating etc. etc. The P&A Manual will also contain flow diagrams which in an easy way list the relevant procedures to be followed when discharging a noxious liquid substance into the sea. The manual is prepared in accordance with a layout given in appendix 4 to MARPOL Annex II and will as minimum contain following sections: Section 1. Main features of MARPOL 73/78, Annex II Section 2. Description of the ship's equipment and arrangements Marstal Navigationsskole April 14

171 171 Section 3. argo unloading procedures and tank stripping Section 4. Procedures relating to the cleaning of cargo tanks, the discharge of residues, ballasting and deballasting Section 5. Information and procedures. Section 5, Information and Procedures shall contain: Table 2: Addendum A: Addendum B: Addendum : Addendum D: argo tank information Flow diagrams Prewash procedures Ventilation procedures Additional information and operational instructions when required or accepted by the Administration. Extract from a P&A Manual: The small chemical tanker ERRIA MARIA. Below is shown an example on prewash information. Marstal Navigationsskole April 14

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174 Example The ship has unloaded a cargo of Rapeseed oil, pollution category Y at an unloading temperature of 15. At 15 the viscosity of the rapeseed oil is higher than 50 mpa s wherefore the cargo is considered as being igh viscosity Using the first flow diagram in Addendum A, - we end up in box: DP 1(a) or 1(b) DP 1(a): DP 1(b): The cleaning and disposal procedure could then be: Strip the tank and apply prewash. Discharge prewash to shore reception facility. Then wash tanks to commercial standards. Dispose of tank cleaning water more than 12 miles from nearest land at a ship s speed of not less than 7 knots, water depth more than 25 metres using underwater discharge. Or the cleaning and disposal procedure could be: Strip the tank and apply prewash. Discharge prewash to shore reception facility. Apply subsequent wash and add ballast to the tank. The ballast water is discharged more than 12 miles from nearest land, water depth more than 25 metres. (This procedure is not very common, as many chemical tankers will never carry ballast in their cargo tanks). Example 2 The ship has unloaded a cargo of Rapeseed oil, pollution category Y at an unloading temperature of 30. At 30 the viscosity of the rapeseed oil is lower than 50 mpa s wherefore the cargo is not considered as being igh viscosity Using the first flow diagram in Addendum A, - we end up in box: DP 2(a) or 3 DP 2(a): DP 3: The cleaning and disposal procedure could then be: Strip the tank. Then wash tanks to commercial standards. Dispose of tank cleaning water more than 12 miles from nearest land at a ship s speed of not less than 7 knots, water depth more than 25 metres using underwater discharge. Or the cleaning and disposal procedure could be: Apply ventilation procedures in accordance with the P&A Manual s addendum. (This procedure will of course not be relevant for a cargo such as rapeseed oil as the vapour pressure is much lower than the required 5 kpa (50 mbar) at 20 ). MARNAV s remarks: For DP 3 there is an X in line 5 saying: Ballast tanks or wash tank to commercial standards. This must be an editorial error as it makes no sense first to remove all cargo residues by ventilation and then afterwards wash the tank with water. Furthermore it is not stated how to dispose of that water! Marstal Navigationsskole April 14

175 175 As the two examples show it is quite simple to follow the requirements from MARPOL Annex II as far as discharge of residue/water mixtures is concerned if the instructions in the P & A Manual are watched closely. It should always be taken into account that there may exist some local restrictions that could go beyond the minimum requirements given in MARPOL. So when in doubt - always check with the local agent or local authorities for special conditions for discharge of residue/water mixtures containing noxious liquid substances. Residues left over in tank after unloading fish oil from TDW chemical tanker Marstal Navigationsskole April 14