1 2. COURSE INFORMATION ‘This course will lead to Tankerman Highest Grade - Chemical. The kourse entering form] has to be mailed or send by fax to Seagull A/S as soon as possible. You will get a unique student ID back and this must be used on all correspondence with us. A 9-part task follows the course including both theoretical and practical tasks. The practical exercises are important to complete. These tasks must be mailed to Seagull A/S. Task 1: Chap. Task 2: Chap. Task 3: Chap. Task 4: Chap. Task Task 6: Task 7: Task 8: Task 9: CRU Auaune The examination is shore based. After completion of the course and all the tasks have been answered and sent to Scagull AS, you can mail the examination entering form] to us. After Seagull A/S has received the entering form you will be informed where and when the examination is to be arranged. Take an active part in the course and work hard with the theoretical and practical statements given throughout the course. If there are any doubts during the course, contact Seagull A/S responsible instructor. This training course is approved by NMD and is in accordance with STCW 95 regulation V/1, paragraph 2.2 except fire fighting course, and ref. STCW 95 regulation V/1.1 and STCW 95 Regulation V/1, paragraph 2.2 and A-V/T 15 - 21 ‘We recommend that you take all the tasks even if you are not participating on the course.Important 1, Remember to mail the course entering form. 2, Remember to mail the tasks and the print reports following the course, 3. Remember to mail the examination entering form, when ready. Mail address: Seagull A/S, Gamleveien 36, P.O.Box 1062, 1N-3194 Horten, NORWAY. Mark the envelope or email with task number Phone no.: +4733 03 09 10 Fax no.: 447 33 04 6279 Email seagull@sgull.com GOOD LUCK!Chapter 1 INTRODUCTION Transportation of Chemicals in Bulk (Tankerman Highest Grade) Department/Author: Approved by: Kjell Vagtberg Erk Frette Seagull Seagull 20607 SEAGULL AS All rights reserved No part of this work covered by the copyright hereon may be reproduced or otherwise copied without prior written permission of SEAGULL AS Gesu muse 5 Transportation of Chemical in Bulk ‘DOCUMENT STATUS. FlesK6-Trinngt-Manualrog underag\Tankor Operation - ChemicalRevislon 2007101 Advanced Chemical CompendumiChapt.04 Inrosueton doc Issue No. [Date/Year_ Inc. by Issue No. [Date/Year_[inc. by 1427B 05. June 07 | KV CHANGES IN DOCUMENT Issue Paragraph Paragraph Heading! No. No. Description of Change B Updated in accordance with new regulations. muse 5 Transportation of Chemical in Bulk “TABLE OF CONTENTS Section Page INTRODUCTION... 1. 4.1. THE course. 1.2 CARGOES IN CHEMICAL TANKERS, 1 3 1.2.1 Cargo Types. ss so 4 1.2.2 _ Structure of Rules and Regulations for Chemical Tankers. 5 1.3. Cargoes in chemical tankers 6 1.3.1 Petrochemical Products. 7 1.3.2 Feedstocks and basic chemicals. 9 1.3.3 Production and use of liquid chemicals. 9 134 Ethylene uw 1.3.5 Propylene nun ss so so sone 1 1.3.6 BULAMIONE oem nnsnnnnnnnse ss ssn sven ID 1.3.7 Aromatics. 1B 1.3.8 Coal tar products. 4 1.3.9 Toluene. 16 1.3.10 Eylen@S.o0..0.n . so sven 16 1.3.11 Methanol or methyl alcoho... ol 1.3.12 Phenol 7 1.3.13 Styrene monomer. 7 1.3.14 Molasses and alcohols... ' sve IT 1.3.15 Molasses 18 1.3.16 Fermentation alcohols. ss so se 18 1.3.17 Wine making and brewing. 8 1.3.18 Vegetable oils and animals fats 9 1.3.19 Vegetable oils 20 1.3.20 Oilseeds used mainly for edible purposes 21 1.3.21 Oilseeds used for edible and other industrial purposss..... 23 1.3.22 Oilseeds used mainly for other industrial purposes. m4 1.3.23 Animal fats and oils. 25 1.3.24 Lard. 25 1.3.25 Beef and mutton tallow. 25 1.3.26 Fish oils.. a - 25 1.3.27 Heavy chemicals so soe 25 muse 5 Transportation of Chemical in Bulk mn1. INTRODUCTION 4.4 THE couRsE Training and the STCW 1995 Convention The standards of competency that have to be met by seafarers are defined in Part A of the STCW Code in the Standards of Training, Certification and Watchkeeping for Seafarers Convention, as amended in 1995. It sets out the education and training to achieve those standards. Special training requirements for masters, chief engineer officers, chief mates, second engineer officers and any person with immediate responsibility for loading, discharging and cares in transit or handling of cargo on chemical tankers, is detailed in section A-V/1 of the STCW Code. I This course covers the requirements for level 1 and level 2 training required by STCW 95 Chapter V Regulation V/1 — 1.2, 2.2 and Section A-V/1 regulations 15 - 24 For further information please see CBT # 0032 Liquid Cargo Properties Miscopll AS, Transportation of Chemicls in Bulk 14.2 CARGOES IN CHEMICAL TANKERS. + Sea transport of chemicals started with the chemical industries’ rapid growth in the years after the World War 2. + At first, chemicals were transported in bottles or drums on dry cargo ships; larger quantities were shipped in bulk in the deep tanks of these ships. ‘+ As the world’s demand for chemicals increased, the need for a new type of seagoing ship became evident. * The first chemical tankers were converted war-built American oil tankers (T-2 tankers). * Conversion work usually included: = adding bulkheads to provide more and smaller tanks - extending the line system - _ installing additional cargo pumps * In addition to these converted, relatively big chemical carriers, smaller tankers specially designed and constructed for the carriage of “acids” - e.g. sulphuric acid = were built during the early 1950's, the cargo tanks of which were made of special alloy steel, strengthened for cargo densities up to 2.0 kg/. ‘+ In order to carry chemicals of high purity and sensitive to contamination, coating techniques were developed for cargo tanks of mild steel. * The first real chemical tanker specially designed for the carriage of liquid chemicals in bulk was the Norwegian M.T. “Lind”, delivered in 1960; this was the first tanker equipped with stainless-steel cargo tanks. * Amodern chemical tanker has a large number of cargo tanks and is designed for carriage of a wide variety of cargoes. + The cargo-tank section on these modem ships is normally divided into some stainless-steel tanks and some coated mild-steel tanks, each of which is normally equipped with deep-well pumps and a separate piping system. + The term “chemical tanker’ does indeed cover a wide range of designs from quite simple vessels designed for transport of low hazard type chemicals to highly complex vessels designed for transport of a large variety of chemicals and special purpose vessels buill for the transport of a single or a few chemicals. In the following, we shall mainly focus on general-purpose chemical tanker design and operation. Miscopll AS, Transportation of Chemicls in Bulk 31.2.1 Carco TYPES The range of cargoes normally transported by such vessels is often grouped as follows: - Chemicals = Oil products - Animal and vegetable oil - Other substances. However, if one wishes to consider the consequences of rules and regulations on design and equipment of chemical tankers, it may be useful to group the different cargoes according to the extent the various rules and certification requirements apply. The entry into force of MARPOL Annex II has established as an overruling principle: Where it is proposed to carry a liquid substance in bulk, which has not been categorized, the Governments of Parties to the Convention involved in the proposed operation shall establish and agree on a provisional assessment for the proposed operation. Until full agreement among the Governments involved has been reached, the substance shall not be carried. As soon as possible, but not later than 30 days after the agreement has been reached, the Government of the producing or shipping country, initiating the agreement concerned, shall notify the Organization and provide details of the substance and the provisional assessment for annual circulation to all Parties for their information. The Organization shall maintain a register of all such substances and their provisional assessment until such time as the substances are formally included in the IBC Code. For crude oil and oil products this assessment has been done once and for all and the consequential application of Regulations and Certification requirements is straight forward. In terms of safety, the SOLAS requirements for oil tankers apply to products with flashpoint less than 60 Centigrade and the Safety Equipment Certificate is proof of compliance. In terms of marine pollution all oils, regardless of flashpoint, are subject to the MARPOL Annex | regulations and the IOPP certificate is the proof of compliance. For liquid cargoes other than oils, the picture is far less clear. The main grouping of the cargoes is: 1) Cargoes subject to the requirements of the “expanded” International Bulk Chemical Code. In Chapter 17 of the Code these cargoes are listed ("expanded” means the International Bulk Chemical Code with amendments making MARPOL, Annex II requirements part of the Code) 2) Cargoes not subject to the requirements of the “expanded” International Bulk Chemical Code. These cargoes are listed in Chapter 18 of the Code. Cargoes under 1. are those products assessed to possess safety hazards according to the hazard criteria of the Chemical Code or products categorized as X, Y or Z according to the marine pollution hazard criteria given by MARPOL Annex II. Miscopll AS, Transportation of Chemicls in Bulk “It is worth noticing that the chemical hazard criteria include flammability hazards, toxicity (human life), reactivity and corrosivity as opposed to SOLAS hazard criteria, which only considers flammability. Cargoes under 2. are those not found to be hazardous according to the Chemical Code Criteria and which have no marine pollution hazards or very moderate marine pollution effects, i.e. categorized as OS (Other substances) substances according to MARPOL Annex Il criteria. It should be observed that all products under 2. both category D products and Appendix Ill products which have flashpoint less than 60° C are subject to the SOLAS regulations for tankers (fire protection requirements). Products under group 1 are only allowed to be carried under a Certificate of Fitness for the Carriage of Dangerous Chemicals in Bulk (C.O.F.) and it is required that the products permitted are listed in the Certificate by their names. Products in group 2 having pollution hazard category OS only are required to be carried under a separate Noxious Liquid Substance Certificate (NLS) if the vessel does not hold a C.O.F. The requirements to be complied with for obtaining such certificate are purely operational and hence carriage may be allowed on all types of ship, except for those products which have flashpoint less than 60° C or which are required to be carried in vessels of oil tanker standard in respect of fire protection and ship arrangements. Products in group 2 which are non-pollutants may be carried without special certification. However, products with flashpoint less than 60° C are only allowed in vessels of oil tanker standard. Unlike oils the assessment of chemicals and other products is not a finalized process. New substances and mixtures of different substances appear as. bulk cargoes for sea transportation from time to time. In order not to unduly upset the trade IMO has adopted guidelines for provisional assessment of substances and allocation of carriage requirements. Provided sufficient information and data for the potential cargo is available, such assessment may be completed within a few days. 1.2.2. STRUCTURE OF RULES AND REGULATIONS FOR CHEMICAL TANKERS. Both our classification rules and the International Bulk Chemical Code (IBC-Code) are composed of two main parts: 1) A general part containing regulations applicable to all multipurpose chemical tankers. 2) An optional part containing special requirements for some individual cargoes or type of cargoes, ‘A general purpose chemical tanker must satisfy all the requirements of the general part (Sections 1 through 14 plus Section 16 of our Rules Part 5 Chapter 4). The general requirements offer options to choose between in several areas, e.g. tank venting, tank ullaging etc. and the choice has an impact on the allowable range of cargoes. The extent to which a chemical tanker complies with the additional special requirements will further determine the extent of additional cargoes permitted Miscopll AS, Transportation of Chemicls in Bulk 5From the above it is seen that the term “chemical tanker" is non-specific because of the alternatives and options available. In a specification it must therefore be stated which design and equipment options and alternatives are to be complied with, alternatively a list of cargoes for which the vessel is to be designed must be specified A dedicated chemical tanker differs from the multipurpose one in the respect that all of the general regulations need not be fulfilled. This in particular applies to the fire protection requirements, which need not be met for non-flammable products. In terms of classification such a dedicated chemical tanker will not be assigned the general “Tanker for Chemicals” notation, but have a notation e.g. “Tanker for phosphoric acid” or "Tanker for non-flammable chemicals’. 4.3. CARGOES IN CHEMICAL TANKERS. -xamples of cargo names (and synonyms) from the long list of liquid products} ransported in chemical tankers} GENRES ‘oluene diisocy anale ri) LT (MEK) TAT ey amma (Ene AER Miscopll AS, Transportation of Chemicls in Bulk ‘1.3.1 PETROCHEMICAL PRODUCTS This is the classification for chemicals derived wholly or partially from petroleum or natural gas, although this strict definition has now been generally broadened to include the whole range of aliphatic, aromatic and naphthenic organic chemicals no matter what their source, which may be petroleum, coal or vegetable. Petrochemicals such as benzene and naphthalene may be obtained from either petroleum or coal, while ethyl alcohol may be of either petroleum or vegetable ori Petroleum is also considered as a raw material in a number of inorganic chemicals such as sulphur, ammonia and carbon black. Raw petroleum or crude oil is a complex product containing thousands of different compounds of hydrogen and carbon and other chemicals such as sulphur and therefore must undergo numerous refining treatments before the light gaseous hydrocarbons, which form the basis for petrochemicals, are obtained. The first process, which the crude oil must undergo, is primary or fractional distillation. This involves heating the crude oil and since the various hydrocarbons in it have different boiling points, they can be separated out into individual cuts or fractions. These basic cuts are gasoline (the main component of petrol) Kerosene, gas oils and residual heavy fuel fractions. These commodities are known as paraffins and make up the traditional bulk liquid cargoes carried in "product" tankers. They are the "saturated" hydrocarbons and chemically, they are relatively stable and unreactive. Although they do not constitute the most suitable materials for making other substances, they do burn readily, some explosively when vaporized and mixed with air, and hence their value as fuels. Further processes such as thermal and, more efficient, catalytic cracking can be carried out on the residual heavy fuel fractions or gas oils to yield lighter and more volatile, high quality distillates and many light hydrocarbon gases such as methane, ethane, propane, butane, olefins and acetylenes. ‘These gases are the unsaturated hydrocarbons and form the basis upon which the petrochemical industry has been buill. Petrochemicals gave birth to and are the feedstock's for the giant plastics, synthetic rubber, synthetic fibres, agricultural chemicals and detergent industries. Plastics are made from simpler chemicals by the process of polymerization in which single short chain molecules or monomers are combined to form molecules called polymers. The two main groups of plastics are the thermosets and thermoplastics. ‘Thermosets flow like syrup when heated and then can be squeezed or moulded into any shape of form, the shape being made permanent by further heating for a few minutes; after that, they can no longer be melted to make them flow agai ‘Thermoplastics soften when heated and harden again when cooled. Synthetic rubbers are also produced by polymerization and resemble certain types of plastics but are characterized by the particular kind of elasticity found in natural rubber. There are two types of synthetic rubber, the first being the general purpose rubbers which have many of the same applications as natural rubber e.g. tires wire and cable insulation as well as a wide range of domestic articles. Miscopll AS, Transportation of Chemicls in Bulk 1There are also special purpose synthetic rubbers which have been developed for use where some particular quality is highly desirable e.g. resistance to great heat, to oil or corrosive action. They are made from basic hydrocarbons such as butadiene, styrene, acrylonitrile and isobutylene among others. a Fatty Acids/Alcohols mVegOils @ Organic Chemicals DGlycerines, poly- Glycol Carbohydrates Soaps, Detergents Chlorinated Solvents @ Inorganic Chemicals Approximate volumes of the major cargo groups carried The third familiar form of synthetic polymers are the synthetic fibres. There are a great number of such fibres now available for use in textiles, upholstery and fabrics trades; among the more well known are nylon, Orlon, Acrilan and Terylene. The manufacture of these synthetics uses basic petrochemicals as raw materials and the finished products display properties similar to animal and vegetable fibres but also possess various additional properties such as being non-flammable, unaffected by moths, mildew or the action of perspiration, sunlight, heat and water. The majority of synthetic fibres are also chemical resistant. Miscopll AS, Transportation of Chemicls in Bulk ‘‘The most widespread detergents are sodium alkyl benzene sulphonates produced by the petrochemical industry. Detergents are surface-acting agents and derive their cleansing properties from a molecular structure which reduces the surface tension of water and gives it greater “wetting” power. Detergents are now widely used for domestic and industrial cleaning purposes. 4.3.2, FEEDSTOCKS AND BASIC CHEMICALS For many years, both Europe and Japan have used mainly naphtha as the feedstock for the production of the basic chemicals ethylene, propylene and butadiene, known collectively as the olefin family and used as “building blocks” for the paints, plastics, dyestuffs, synthetic rubber and synthetic fibre industries The European chemical industry has traditionally depended upon cheap feedstocks of naphtha, but since prices rose steeply in the 1970s, other forms of feedstock have been used. Particularly attractive as an alternative has been LPG, which has already made a major impact in the Japanese petrochemical industry and has successfully competed with naphtha in European markets. However, supply of LPG has been a problem as producers sort out their production levels and pricing policies. While large LPG, surpluses from Middle East producers were being forecast as late as 1980, these have by and large not appeared, and the considerable number of specialist gas carriers being built against this transport requirement have been a disappointment to their owners. Still being assessed is the arrival in Europe of large quantities of Saudi Arabian naphtha, which could prove very important to he European chemical industry. In Japan the chemical industry is being encouraged to use greater principal feedstock, the argument inevitably devolves upon price. The dominance of naphtha in Japan is however being gradually reduced, which is also the case in the European market, where gas oil and LPG's are making a substantial impact, The situation is completely reversed in the US, where the main reliance is on ethane, propane and butane, less than 20 % of chemical feedstock being made up of naphtha. In the long term especially with the greater interest in coal it is possible that a number of chemical building blocks may derive from this source. Some crude, benzene, toluene and xylene are at present made from coal and work is progressing on improving the process for making ethylene from this fossil fuel. 1.3.3 PRODUCTION AND USE OF LIQUID CHEMICALS The basic petrochemicals are Ethylene, Propylene and Butadiene, all of which are obtained by the cracking of natural gas, or naphtha and gas oil from crude oil. All three of these important basic petrochemicals are transported in liquid form by gas carriers and their sea transport is therefore outside the scope of chemical tankers. Miscopll AS, Transportation of Chemicls in Bulk °(principally wed as direct fuel) Saturated hydrocarbor Gas (Paraffin) Diesel oil Jet fuel Heating oil Low-botling- point solvents Otefines Avetglemes fallenes) caikynes) (ee ethylene) { — HH vlc Courtele rere ‘Acrikan olythene ‘Ori Palystyrone Solvents Symtctic rubbers ‘Acctle aides Detcrgonts Chloroton ahylene gio (antifreeze) Butadiene (for syatetle rubbery Solvents (eg trihboroethylene) Esters Benzene Solvents Routes from crude oil and natural gas to chemicals Miscogll AS Transportation of Chemicls in Bulk wo1.3.4 ETHYLENE This is the simplest member of the olefin family, the largest volume organic chemical and is sued in more than 30 % of all petrochemical products. Because of its unsaturated nature, ethylene is very reactive and it has become one of the main building blocks of the petrochemical industry. The principal source of ethylene in Europe is the steam cracking of naphtha, while the United States traditionally has obtained its ethylene supplies from natural gas liquids. The main attractions of ethylene to the chemical industry have been the ready availability of this feedstock, a reasonable cost and high purity. More than two-thirds of its utilization is for the production of polymers, a fast expanding sector. 7 07] GSES EEE EEE PEPER TF TEGAN So anti-freeze Tenn In me Sa laslics ce 171 mB iE EWE: Int lasticizerg STE ELSES ETIERSEIE EER ethyl chloride trol adtive: Te petrol adaitives} ‘au mae Miscopll AS, Transportation of Chemicls in Bulk uw1.3.5 PROPYLENE Propylene is a co-product of the ethylene production in the steam cracking of naphtha. Propylene is the second member of the olefin family and is currently a high growth chemical because of the high demand for polypropylene, a principal derivative. Crude propylene is also obtained from oil refinery gases in a state, which needs purifying for chemical production. The table below lists some of the major propylene derivatives. In Europe, propylene was always produced as a co-product of ethylene, independent of demand. As a result, there was always an over-capacity and propylene prices remained low. Attempts were made to make high severity crackers with high ethylene/propylene ratios; however, technological problems made such crackers unfeasible. In the interim, demand for propylene has grown until now it enjoys higher growth rates than ethylene. There are two main reasons for this change in the fortunes of propylene: 1.Demand for polypropylene is high and new capacity authorizations are going ahead. It is the most versatile and lowest cost olefin-based polymer for the manufacture of a variety of synthetics. 2.An improved catalyst is available for acrylonitrile production, which will allow greatly increased production of this commodity at existing plants for low capital expenditure. Since propylene is dependent on ethylene production, if ethylene forecasts are over- optimistic, propylene production could be hit. However crude propylene is also obtainable form cil refinery operations and can be used as a chemical feedstock after purification. Furthermore, doubts on the future availability of light naphtha are resulting in the planning and construction of new, more flexible ethylene crackers to run on heavier fractions which gives increased potential for propylene production. 1.3.6 BUTADIENE Butadiene is the most widely used of all the synthetic rubber raw materials and is one of the by-products of the stem cracking process. A number of rubbers are derived from butadiene, the commonest of which is styrene butadiene rubber, which has the widest range of uses, including shoe soles, waterproof boots, sponges, carpet underlay, garden hoses, tyre treads and rubber dinghies. With acrylonitrile, butadiene forms nitrile rubber used in products, which must combine elasticity with resistance to oil and grease, e.g., oil hose linings. Polybutadiene is also used extensively in car and truck tyres. A further use of butadiene is with acrylonitrile and styrene in the production of ABS plastics-terpolymer or plastics “alloy”. ABS is used for engineering components, casings, car body panels, in aircraft, and for heads of golf clubs. Miscopll AS, Transportation of Chemicls in Bulk 2Product Use polypropylene plastic mouldings fibres films. acrylonitrile synthetic fibres synthetic nitrile rubber plastic propylene oxide detergents paints resins: polyesters polyurethane foam gas scrubbing isopropanol paints plasticizers motor fuels ‘cosmetics cumene (converted into. phenol and acetone) phenol pharmaceuticals plastics resins detergents insecticides herbicides lubricating oil additives fibres: nylon Acetone paints Brake fluids textiles explosives plastics The usage of various propylene der 1.3.7 Aromatics The aromatic products, benzene, toluene and xylene (BTX), are used as intermediates for the production of chemicals, as solvents and for gasoline blending, The majority of aromatic production in Europe is petroleum-based, e.g. 89 % of West European benzene capacity is oil-based, and is produced by catalytic reforming Styrene, cyclohexane and, to lesser extent, phenol, are also produced during this process. Miscopll AS, Transportation of Chemicls in Bulk BsOf the three aromatics, xylene is used most extensively in the chemical industry. Mixed xylenes (ortho-xylene and para-xylene) have been used in the manufacture of polyester fibres and films since the 1950s. Aromatics are also used in the production of alkyd resins, unsaturated polyester resins and plasticizers 1.3.8 COAL TAR PRODUCTS Coal, like oil, is chemically a complex substance but unlike oil, it is somewhat deficient in hydrogen and rich in carbon. This not only makes for a lower heating value but also makes it more difficult to convert coal into clean liquid products than it is to refine into such products Moreover, processes developed for one type of coal may not work with another and conversion of coal requires the handling of vast tonnage of the raw material. However, the original industrial source of hydrocarbons is the residual coal tar derived when coal tar derived when coal is carbonised to produce coal gas, and although its importance has been dissipated by the large scale use of petrochemicals, the potential for coal tar products appears brighter now than it has for some time. Coal tar is a black, viscous, thick liquid from which a great number of chemical compounds are derived. The first fraction obtained in the distillation of coal tar contains many aromatics, among them benzene, toluene and xylene. Benzene is the lightest fraction obtained from the distillation of coal tar hydrocarbons. It is a thin, colourless, highly inflammable liquid with a characteristic smell. It is a good motor fuel solvent as well as being a feedstock for other benzene derivatives used in dye, insecticides and plastics production. At a later stage in the distillation process, heavy coal tar solvent naphtha and a naphthalene fraction are produced. The fraction is further treated to yield naphthalene, a white crystalline solid with a important as the starting point for a number of dyes and also as a source of phthalic acid which in turn leads to indigo and to certain resins used in very large quantities in paint Benzene is by far the most important of the aromatics and its principal derivatives are cyclohexane, cumene, ethyl benzene and alkyl benzene. Cyclohexane accounts for approximately 23 % of the benzene usage. The demand for cyclohexane over the next few years in Europe will be strong due to the growth of polyamide fibres and cyclohexane's replacement of phenol in many processes. Ethyl benzene represents approximately 45 % of the benzene production and is used in the manufacture of styrene which in tum is used to produce polystyrene and ABS (acrylonitrilelbutadiene/styrene) resins, both of which should enjoy strong growth rates. Cumene is used to make phenol and alkyl benzene goes toward the manufacture of detergents. Miscopll AS, Transportation of Chemicls in Bulk maCoal Gas| sulfate <4 Panication Getiizes) Coke Pure Coal Gas \distlation Hy ot Pitch om (atSmtia eects) Berne, Tolnene, Xylene Creosote Solvents Motortvel a. Fucis Disinfectants Preservatives Dyer Explosven Phenol types " Naphtalene “lf — or ee ~ Cress ak Eph WN Cyebhiftanet a aa } 1 anid 1 Nstons Aspiein The route from coal to chemicals Already a great deal of research has been carried out and scientists have investigated many possible routes from coal to chemicals with or without fuels as co- products. They include chemicals such as methanol and ammonia gathered from coal gasification processes; aromatics, particularly benzene, from coal hydrogenation; and the production of acetylene by exposing coal to arc-heated hydrogen, Miscogll AS Transportation of Chemicls in Bulk isAlthough early results have been to an extent encouraging, the development of these processes to the necessary level of economy and efficiency is unlikely to be quick or easy. 4.3.9 TOLUENE Toluene is not as important as benzene because of its more limited range of uses. Toluene's main derivatives are benzaldehyde, benzoic acid, toluene, and nitro toluene. It is also used in the manufacture of solvents ant gasoline as well as benzene production through dealkylation. Approximately 75 % of worldwide toluene capacity go to produce benzene, the remainder being for chemical and solvents uses. 1.3.10 EYLenes World demand for mixed xylenes, i.e. ortho-xylene and para-xylene, has been growing at about 6 % per year. Para-xylene first entered the chemical market in the 1950s when it was used to produce dimethyl terephthalate (DMT) and terephthalic acid (TPA) for polyester fibres. Polyester fibres have increased their share of the world fibres market significantly in recent years but is experiencing a significant decline in demand at the moment. A small but growing share of DMT/TPA output goes to polyester film The second major xylene market to develop was the use of ortho-xylene to make phthalic anhydride, one of the most important organic chemicals. Phthalic anhydride is used in the production of phthalic plasticizers, polyesters, alkyd resins and dyestuffs. Ortho-xylene has all but replaces naphthalene as the basic feedstock for this organic chemical. 4.3.11 METHANOL OR METHYL ALCOHOL Methanol is important as an intermediate for organic synthesis. It was originally produced by the destructive distillation of wood and synthesised from natural gas, although the production techniques were costly and inefficient. The most significant technological development in methanol production was the advent of the ICI low pressure process that allowed high-quality, comparatively low cost methanol to be derived from petroleum. Approximately 50 % of the methanol used for chemical uses goes to the production of formaldehyde, which in turn forms a basis for urea resins and phenolic resins. Methanol is also used to produce methacrylate, methyl methacrylate (for plastics), dimethyiteraphthate (DMT), methylamines, methyl chloride and soivents. An uncomplicated cargo capable of transport in ships that are relatively unsophisticated, methanol is one of the basic feedstocks, the production of which is shifting dramatically from the developed chemical producing countries to the new producers of the Middle East, Brazil, Canada and New Zealand, with the former producers all becoming net importers of this relatively low value chemical. Major projects started to come on stream in 1982 and 1983 saw the export of the first large single shipments of methanol from the new facilities of Saudi Arabia. The same year also saw the start-up of a vast methanol facility in Siberia capable of 2500 tons/day, Miscopll AS, Transportation of Chemicls in Bulk 16with a third of its production stemmed for Wester Europe, and first deliveries scheduled for 1984. With the late 1983 price of methanol less tan $ 180 per ton, the new imports would seem certain to keep this feedstock low priced and readily available from a variety of sources Methanol is also an alternative fuel source to liquefied natural gas (LNG) but methanol plants are costly and bulk shipments by sea are economical compared to LNG only when the distances are great, say from the Persian Gulf to Japan, the USA or Europe, 4.3.12 PHENOL Phenol is a key product in the chemical industry. The major source of Phenol is the benzene derivative, cumene, and acetone is produced as a by-product. Cumene is a relatively inexpensive feedstock, which can be produced by obsolete refinery units, which have been converted. The USA and Europe have in the past been responsible for the bulk of the phenol produced and trade has always been active especially the intra-European trades. This was because a number of European countries did not produce sufficient phenol to meet domestic needs. In 1978 Germany, Italy and the UK were the principal exporters in Europe with a total of 272.000 tons though the trade was mainly regional. Exports from the USA have ceased and those of Japan have increased to 93.000 tons, two-thirds of which was for other Far Eastem countries. 1.3.13. STYRENE MONOMER Polystyrene and expendable polystyrene account for about two-thirds of the world's consumption of styrene with ABS resins (acrylonitrile/butadiene/styrene) butadiene rubber taking most of the remainder. In a similar fashion to methanol (although it is a far more valuable chemical, with a current price of about $ 700 per ton) styrene is one of the basic chemicals the production of which is moving rapidly form high cost areas to production locations nearer the source of raw materials. While there is a current over capacity problem in the chemical industries of Japan, the US and Western Europe. The prospects of this surplus plant being reactivated is slight, with some 1 million tons of new styrene capacity under construction in Saudi Arabia, Libya, Kuwait and Canada, all of which will be able to produce product at a more economic price than that in the traditional chemical producing countries. 1.3.14 MOLASSES AND ALCOHOLS This category sometimes referred to as carbohydrate derivatives are produced by fermentation. The latter are associated with the brewing and winemaking industries. Fermentation is a process by which organic compounds are broken down or changed by the agenoy of living organism or of ferments (enzymes) produced by them. The end products are alcohols and carbon dioxide and although large quantities of alcohol are now made from ethylene in the petrochemical industry, there are still a great number of alcohols which are carbohydrate-derived. Ships, which carry these commodities, are required to possess the same high standards for the maintenance of cargo quality as carriers of petro- and heavy chemicals. Miscopll AS, Transportation of Chemicls in Bulk n1.3.15 MoLasses ‘The two types of molasses commonly carried in bulk by sea are cane and beet molasses. Both types take the form of thick brown syrup and are produced during the sugar refining operations by removal from the sugar crystals. Cane molasses or black strap, which comes from raw cane sugar, is the heavier of the two with its final composition depending on the country of origin, cane maturity and methods of manufacture. Beet molasses is processed from the roots of the sugar beet and is a less viscous molasses than black strap. The better grades of both types of molasses can be fermented into alcohols such as rum and can also be used in treacle manufacture. Other uses include animal feedstocks and the production of yeast and organic chemicals. Cane molasses is produced in the fertile tropical and semi-tropical regions of the Caribbean, Southern USA, Central and South America, East Africa, Asia and Australia. In some countries the local consumption of cane molasses for animal feed, rum or alcohol is small, leaving a large proportion available for export. The main consumers of cane molasses are principally the United Kingdom, Westem Europe, USA and Japan. Beet molasses is grown in the more temperate zones of the United Kingdom, Western Europe, USA, Easter Europe and the USSR. It is in special demand for the manufacture of products such as yeast, citric acid and monosodium glutamate. Beet producing countries tend to consume almost all their own production, some countries using it for fermentation of alcohol and animal feed. The USSR and Eastern Europe are self-sufficient in this type of molasses and in general, exports of beet molasses world-wide are negligible. Molasses is a low value product and the sea borne shipment of the commodity is a restricted market. Only a small number of operators world-wide handle sizeable amounts of the product, these being carried in epoxy or uncoated tanks suitable for products for a specific gravity of 1.4. 1.3.16 FERMENTATION ALCOHOLS The most common alcohols are ethyl, methyl and propyl alcohols (ethanol, methanol and propanol). Although methanol and propanol are mainly produced by the petrochemical industry substantial amounts of ethanol are still produced by fermentation of starch. Ethanol is a colorless liquid freely miscible with water. In its original state it can be used as a fuel or a solvent (methylated spirits) but it is also an important raw material for chemical manufacture. Ethanol as well as the other alcohols can be oxidized to forma Aldehydes and then to carboxylic acids, with which they also react to form esters. In this way, acetic acid is derived from ethanol for use as a solvent, and, by reaction with ethanol, to produce ethyl acetate. One common ester formed by cellulose and acetic acid is cellulose acetate, which is familiar as a thermoplastic moulding compound (telephones, packaging, film and buttons), as a manmade fibre (Tricel) and as a lacquer. 4.3.17 WINE MAKING AND BREWING Wine is the fermented juice of the fresh grape. After picking, the grapes are crushed or pressed and placed in vats to ferment. Most table wines contain 6 - 14 % alcohol by volume while fortified wines such as sherry and martini vermouth have further alcohol added. Miscopll AS, Transportation of Chemicls in Bulk isFrance, Italy and Spain have extensive vineyards and annually export large quantities of wine in bulk to be bottled by the importer. Argentina, Portugal, the USA and the USSR also produce large amounts of wine. Seagoing vessels carry wines and fortified wines not exceeding 27° proof. Brewing is the production of alcoholic malt beverages by fermentation: they contain 2 - 7 % alcohol by volume. The temperature at which fermentation is allowed to occur determines the type of beer to be produced. Lower temperature fermentation causes yeast to sink to the bottom of the vat and produces lager while higher temperatures produce heavier beers. There are extensive brewing industries in most countries, especially Britain, Germany, Denmark, Czechoslovakia and the USA. Certain lagers and dark beers such as Guinness are exported in bulk by sea 1.3.18 VEGETABLE OILS AND ANIMALS FATS ii, fats and vaxes occur in plants and animals as esters of alcohol and strait-chain carboxylic acids. They are insoluble in water and oily or greasy to the touch. Their composition is quite different from mineral oil, e.g. petroleum, which are almost completely composed of hydrocarbons. Although oils are liquid at room temperature and fats are solid, both are, in general, esters of an alcohol called glycerol and a variety or organic acids known as fatty acids (e.g. palmitic, stearic, oleaic). The fat contained in animal and vegetable oils, along with proteins, carbohydrates, vitamins and minerals, is one of the main nutrients required by the human body. Fat performs a variety of functions essential to good health. It is a highly concentrated source of energy, which is needed to promote activity and to keep the body at the right temperature. It is a carrier of vitamins A, D, E and K. Fats are also needed to supply the substance known as fatty acids. These are essential in that the body needs but cannot synthesize them, so that they must be present in the diet. Essential fatty acids reduce cholesterol in the blood and promote the building of healthy skin cells. Fatty acids can be either saturated (lauric; myristic; palmitic — present in nearly all known fats; stearic) or unsaturated) palmitoleic; oleic — the most common of all fatty acids; linoleic). Fats or oils containing saturated fatty acids are generally in the solid form and are required in the manufacture of soap and margarine, while fats or oil containing unsaturated fatty acids usually are liquid at room temperature. The current world trade in oils and fats is a comparatively new phenomenon in historical terms. This trade is almost entirely a development of the 20" century technology. Although the substitution of petroleum-based products freed large quantities of oils and fats for human consumption, new industries based on the manufacture of chemicals from fats have sprung up over the last forty years. Processes devised to remove pure single fatty acids from fats have resulted in production of long-chain alcohols, amines, amides, esters, nitriles, and ketones. These substances or intermediates in tum were used to manufacture detergents, plasticizers, special lubricants, polyamide resins and special gel paints. The manufacture of margarine and soap has also benefited by the development of a process called hydrogenation. Production of these commodities required solid fat but at the turn of the century animal fats were in short supply. Hydrogenation, however, made it possible to use vegetable oils, which had previously been considered to be too soft, for these processes. Miscopll AS, Transportation of Chemicls in Bulk »1.3.19 VEGETABLE os Vegetable oils are derived from seeds of plants which grow in a wide variety of places throught the world. Although several hundred plants types are known to have oit-bearing seeds, only about a dozen are significant commercially i.e. soya bean, groundnut, cottonseed, sunflower, olive, rapseed, sesame, coconut, oil palm, linseed, castor and tung. The chief importance of vegetable oils lies in their food value since they are essential for a balanced diet. The current world production of vegetable oils is about 42 million metric tons a year, being about two-thirds of all types of oils and fats. Edible vegetable oils can be consumed in various ways, either in their natural liquid form as cooking oils or in spreadable form such as margarine. Vegetable oils are used in other food industries for the manufacture of cooking fat and oils, salad dressing and ice cream. In addition to their value as a source of oil, several of the plants have a high protein content, in particular soya bean and groundnut. For this reason, the residue, after oil removal, in many cases provides animal fodder. Outside food manufacture, vegetable oils are used in a wide variety of applications in industry, from soap manufacture (the most important) to the production of paints, varnishes, lubricants and plastics. All oils used in industry must be refined and the degree of reining depends on the particular end use. Although no vegetable oil is equally suitable for all of the possible end uses since each oil has unique characteristics, it is possible divide vegetable oils roughly into three broad groups i.e. a) Those used mainly for edible purposes b) Those suitable for edible and industrial purposes ©) Those suitable only for industrial purposes (A) DRYING (B) SEMI-DRYING (C) NON-DRYING Linseed Oil Cottonseed Oil Lard Oil Tung Oil Sesame Oil Olive Oil China Wood Oil Maize Oil Groundnut Oil Soya Bean Oil Wheat Oil Castor Oil Hempseed Oil Sunflowerseed Oil Rape (Colza) Oil Walnut Oil Codliver Oil Almond Oil Otticea Oil Cod Oil Rice Oil Perilla Oil Herring Oil Sperm Oil Rubberseed Oil Shark Oil Seal Oil Miscopll AS, Transportation of Chemicls in Bulk 2Poppyseed Oil Whale Oil Palm Oil Tall Oil Sardine Oil Palm Kernel Oil Ete. Japanese Fish Oil Coconut Oil Ete. Tallow Oil Ete. ‘Types of vegetable and animal oils 1.3.20 OILSEEDS USED MAINLY FOR EDIBLE PURPOSES Soya bean The soya bean originated in Eastern Asia and is still widely cultivated in China, Korea and Indonesia, although today the world's chief producer is the USA. During the last twenty years, production of soya beans in the cotton and maize belt of the southern US has increased dramatically. Largely because of the increased output in the USA, soya bean has recently become the world’s leading source of vegetable oil, even though the oil content is relatively low (13 % to 20 %). Soya oll goes into margarine, cooking fats and salad oils. Soya beans are also very rich in protein (41 to 50 %), containing twice as much as beef. The meal, which is left after the oil has been extracted therefore, makes nutritious animal fodder. Because of its high protein content and cheapness compared with sources of animal protein, extensive research is being carried out in developing new soya products for human consumption. In the Far East, soya beans are a staple food. They are boiled, roasted, milled into flour and used to make soya sauce and soya bean milk. Soya oil is also used in the manufacture of soap and cosmetics, insecticides and paper coatings and as a drying oil in paints, varnishes and printing inks. Groundnut The groundnut is also known as the monkey nut, peanut, earth-nut and arachis nut. Originally grown in the West Indies and South America, it is now cultivated in most tropical and sub-tropical countries. The pods on the small annual groundnut plant turn down into the ground to a depth of about 5 cm, where they swell and ripen. Groundnuts have an oil content of approximately 45 % and the main uses of this oil are in the manufacture of margarine, cooking fats, salad oils and ice cream. After extraction the residue provides a protein-rich cake for animal feeding. Groundnuts are also consumed direct, representing an important staple food in the producing countries when stewed with meat or roasted. The groundnut plant becomes hay for fodder once the nut has been removed. Cottonseed Cottonseed is essentially a by-product since the cotton plant is grown primarily to produce cotton fibre. Even though the cotton plant has been cultivated for several Miscopll AS, Transportation of Chemicls in Bulk nthousand years, it was not until late in the last century that serious commercial uses were found for the cottonseed. Cotton is produced in tropical, sub-tropical and warm temperate climates, which have a distinct wet and dry season. Cottonseed oil, which makes up between 15 and 25 % of the seed itself, is used in the manufacture of margarine, cooking fats and oils and salad dressings. The cake residue left after the oil has been processed is a useful source of animal fodder, as are the seeds themselves. Both can also be used as fertilizers while the hulls remaining after treatment provide fodder and fuel. Sunflower Several varieties of this large yellow-petalled flower are cultivated throughout the world, the most common reaching heights of between 1.5 and 2.5 m. The sunflower originated in Central America, but is now grown extensively in regions such as the USSR, South America, southern and central Europe, and Canada. Until the 1960s the oil content of the sunflower seed ranged from 20 to 32 %. This figure has been significantly increased in recent years by the evolution of new strains in the Soviet Union and eastern Europe with an oil content of 40 % or more. About four-fifths of world production is now believed to be of these high-yielding varieties. Sunflower oil is used in the manufacture of margarine, cooking oils and fats, and salad oils. In a less-refined state, it goes into soaps, paints and lubricators. After the oil has been taken off, the residue is made into cake for cattle food. The flowers themselves give a yellow dye, while in Russia the stalks are burned and high- grade potash salts extracted. Olive Although the olive tree has no particular soil requirements and can grow on the poorest of land, climatically it needs Mediterranean conditions, i.e. warm dry summers without excessively high temperatures. The large olive producers are centered on the Mediterranean area, Italy being the largest producer but not exporter. Although olive oil is not of tremendous importance commercially, it is the finest of all vegetable oils and is therefore greatly in demand as a table oil for salads and for preserving. The first crushing gives the highest grade oil, which does not need refining. The oil content of the plant is about 15 %. From the residue inedible oil is extracted, known commercially as sulphur oil, olive kernel oil or "sauces". This inedible oil is widely used in soap-making, wool combing and other industrial processes. Production of edible olive oil varies from year to year since it is so dependent on climatic conditions during the pollination period. Some olives are grown for direct consumption as table olives. Generally, these olives have relatively low oil content. Rapeseed Rapeseed is the name given to the seed obtained from several plants of the brassica family. Although the crop is still not important in international trade, there are signs that rapeseed oil is regaining importance after a marked decline between 1860 and 1945. China and India are important areas of production Rapeseed yields 35 to 40 % edible oil for use as table oil and for cooking. Agai after the oil has been extracted the remaining cake can be used in limited amounts as animal fodder. Miscopll AS, Transportation of Chemicls in Bulk 2Sesame Sesame has been popular crop in China and India for many centuries. Today it is cultivated in most tropical and sub-tropical areas, China and India being the leading producers. Current world production is about 1.9 million tons. There is currently no significant international trade in oil from the sesame seed. Sesame is an annual plant particularly suited to a peasant type of agriculture, since it will grow on poor soils and the crop is easier to grow by hand than by mechanical methods. The oil content of sesame is quite high at approximately 50 %. Sesame oil is used for much the same purposes as olive oil 1.3.21 OILSEEDS USED FOR EDIBLE AND OTHER INDUSTRIAL PURPOSES Coconut The coconut palm is a perennial of unknown origin. It is thought to have spread across Polynesia from the Indian Ocean, and today it is found in the coastal belts of all tropical countries. The palm varies in height from between 18 and 30 m and produces fruit, which when growing looks like a smooth, green rugger ball. When fully mature the coconut has a fibrous outer husk and an inner kernel. The kemel when dried is known as copra, and it is from this that coconut oil is extracted Copra yields about 63 % oil. Local inhabitants use this oil for cooking and lighting and as a hairdressing. Industrally, large quantities are required throughout the world in the manufacture of margarine and cooking oils and fats. It is also used, to a lesser extent, in soaps and lubricants. After oil extraction, residue cakes can be used as animal fodder. A certain amount of fresh kernel is made into desiccated coconut for the confectionery trade. Another minor source of oil in coconut is the green skin or paring. Production of parings oil has become quite important in Sri Lanka. In recent years the Philippines has increased its production substantially and now accounts for over half the world's output Oil Palm The oil palm is a perennial plant indigenous to tropical West Africa. Today it is grown in the equatorial coastal regions of Africa, Indonesia and Malaysia. The tree itself may reach 18 m in height while the fruit grows in bunches averaging 13 to 18 kg in weight and varies in colour between deep orange and reddish brown. ‘Two kinds of oil are obtained from the oil palm. ‘The structure of the individual palm fruit resembles that of the coconut, with a thick, fibrous layer of pulp on the outside (the pericarp) and a hard kernel. From the pericarpp comes palm oil, and from the inside, palm kernel oil, a harder substance rather like coconut oil Palm oil is used locally for cooking and is exported for use in the manufacture of edible fats. Kernel oil is supplied primarily to manufacturers of margarine, cooking oils and fats, sugar confectionery and in a lesser degree to manufactures of soap. If properly cultivated, the oil palm produces higher yields per acre than any other oilseed crop. Malaysia and Indonesia are the leading producers of both types of oils. Miscopll AS, Transportation of Chemicls in Bulk 21.3.22 OILSEEDS USED MAINLY FOR OTHER INDUSTRIAL PURPOSES seed Linseed is the seed of the flax plant. The plants cultivated for seed are often of a different variety form those cultivated for fibre, with a shorter stem, though in many parts of Europe a dual variety is now grown. Linseed for oil production is grown extensively throughout the eastern and western hemispheres. Linseed has an oil content of 30 to 40 %. The oil is one of the most important in industry. It is a drying oil, i.e. on exposure to air it oxidizes and becomes an elastic film. Its principal uses are in the manufacture of paints, varnishes, linoleum, oilcloth, printing inks and soft soaps while the cake residue provides a valuable animal fodder. Castor seed The castor plant grows wild in most tropical and sub-tropical regions but is cultivated as a perennial in the more important producing countries such as India, Brazil and China The oil content of the castor plant is about 45 %. Its most important uses now are probably in the manufacture of plastics, nylon and paint. It is also an ingredient for high-grade lubricants, soaps, varnishes for the printing industry and resins. Castor seed is also a source of sodium ricinoleate, used by dentists to treat gum troubles. Until recently the cake, which remained after crushing could only be used as a fertiliser because it was poisonous, but it is now possible, thanks to research in Brazil, to eradicate the poison and use the cake as animal fodder. Tung oil Tung oil comes from the nut kernels of two trees, “aleurites fordli" and “aleurites montana". The former is more widely cultivated and grows mainly in warm temperate climates such as the south-central provinces of China, the southem USA and north-east Argentina. The “aleurites montana” requires a more tropical climate and grows in south-east Asian countries. Tung trees are in full bearing at about 10 years and are productive for a further 30 years or so. Tung oil is used, often after thinning with other oils, in the manufacture of waterproof varnishes, wall and floor paints, enamels, resins and plastics, lacquers and inks. In general vegetable oils are exported from either the agricultural areas of the Western Hemisphere or the tropical areas of the Far East and Africa. Importers are mainly the developing countries, which do not produce the raw materials necessary for making soap, cooking fats, margarine, etc. There is also a fairly consistent flow of products such as soya bean oil, coconut oil, palm oil, etc. from the production areas into Europe and North America. The movement of these products into Japan has been increasing over the past few years and is expected to grow even more considerably. Miscopll AS, Transportation of Chemicls in Bulk “1.3.23 ANIMAL FATS AND OILS The animal fats that are shipped in bulk internationally are lard, beef and mutton tallow and various fish oils. Animal fats are usually extracted from carcasses by a process called rendering whereby fat is liberated from the cells by boiling or steaming and collected by skimming the vat surface. 1.3.24 LarRD Lard is the rendered or melted fat of the hog. tis creamy white substance with a large plastic range and has the highest shortening value of any plastic (semi-solid) fat. Lard oil is clear, colourless oil pressed from pure lard. It is used in cutting oils, and as a nutrient for cultures in antibiotic production. 1.3.25 BEEF AND MUTTON TALLOW These tallows are the rendered animal fats from cattle and sheep. Tallow enjoyed a booming trade when candles and tapers were the only method of lighting. When gas lighting replaced curdles the big market for tallow became soap manufacture. Both beef and mutton tallow are still used extensively in soap making, having survived the inroads made by synthetic detergents. Tallow is also used as a 10 % ingredient of animal foodstuffs while beef tallow in particular, is still used in candle making. The largest tallow exporters are the USA, Australia, New Zealand and Canada while there is also a significant trade in small- quantity shipments widely spread throughout the world Beef and mutton tallows are still used in margarine production although not as extensively as earlier in the century due to their replacement by vegetable oils. Tallows are also used in soap manufacture and the demand for tallows for this use is likely to be strong in developing countries. In the West however, the major expansion in the detergent field is in soapless detergents based on mineral oils; hence demand for tallow in these regions should slip. Lard is used not only for food and detergent applications but also for pharmaceuticals and related chemical products. Demand for lard is likely to remain static. 1.3.26 Fish ons A number of marine oils are processed and transported in bulk for use in a wide variety of end-products. Sardine menhaden, herring, cod, seal and whale provide the majority of the world's fish oils. Virtually all of these oils are used in leather currying and paint manufacture while herring oil is used in margarine production. Fish oils are also used in soaps, fiber dressing, greases, resins and, in certain cases, as lube oil for delicate machinery. 1.3.27 HEAVY CHEMICALS The heavy chemicals are so called because they are produced and transported in large quantities and they are utilised by virtually every manufacturing industry. Although other petrochemicals are also transported in bulk, this section deals specifically with the inorganic chemicals such as mineral acids. Miscopll AS, Transportation of Chemicls in Bulk 2sSulphuric acid Sulphuric acid is manufactured in enormous quantities all over the world as one of the cheapest and most useful industrial chemicals. Sulphuric acid consumption is a significant indication of a nation’s industrial activity. It is a powerful dehydration agent, a valuable electrolyte and a strong oxidising agent and solvent in which many important reactions can be brought about. It is used in weak solutions to control acidity or alkalinity while strong concentrated fuming acids are prepared for the manufacture of drugs, explosives and dyes. Sulphuric acid can be made in various grades. High purity grades are utilized in the rayon and pharmaceutical industries and low grades are used in the manufacture of super-phosphate and ammonium-sulphate for the fertilizer industry. The same batch of acid can, in fact, be used for several purposes in succession. The principal uses of sulphuric acid are outlined below: Manufacture of phosphate fertiliser from rock phosphate by converting insoluble rock phosphate into soluble phosphate using 70 % concentration (low-grade super phosphate). Manufacture of explosives such as nitro-cellulose and trinitrotoluene (TNT) where it is used as a dehydrating agent. Manufacture of plastics such as nitro-cellulose and various synthetic fibres such as rayon Manufacture of other acids. Concentrated sulphuric acid may be used in producing hydrochloric, nitric and other acids. In each case a salt of the acid to be prepared is heated with sulphuric acid. "Pickling" metals. In this process the sulphuric acid is used to remove the coating of oxide from the surface of iron or steel before the metal is plated, coated or galvanized. Purification of petroleum. In this process the sulphuric acid is used to char and remove many organic impurities. In storage batteries. A solution of sulphuric acid is used as an electrolyte in the storage battery. Sulphuric acid is carried in varying concentrations, the most common being 93,2 %. In this concentration it is a syrupy oily liquid sometimes called “oil of vitriol". Another popular concentration for shipping is 78 % sulphuric acid. Acids of 77 % Concentration and above do not react with dry mild steel or stainless steel at normal temperature but diluted acids of less than 77 % concentration react with and corrode most of the common metals. Concentrations of less than 50 % must be carried in rubber-coated tanks. Fuming sulphuric acid contains a concentration of between 20 and 65 % of sulphur trioxide in sulphuric acid and is very corrosive to most metals when water is present. Mild steel and stainless steel are suitable containment materials if the tanks are kept free from moisture. Spent sulphuric acid or sulphuric acid which has been used for a chemical process is also carried by sea. The impurities which it contains will vary depending on the process so that shippers must Miscopll AS, Transportation of Chemicls in Bulk %consult various authorities to make sure of all the hazards involved with that particular grade of sulphuric acid. Sulphuric acid is produced by burning sulphur to give sulphur dioxide, which combines with oxygen in the presence of a catalyst. Since sulphuric acid is made from cheap raw materials, sulphur, air and water, it is the cheapest of all the aids. About 90 % of all sulphur go into the production of sulphuric acid and most of this is subsequently consumed by the phosphoric fertilizer industry. As the two markets are interrelated it is essential to examine the production and movement of the raw material in order to see the resulting pattern, for sulphur acid. There are three main sources of sulphur: 1, Brimstone - any type of sulphur produced in its elemental form. 2. Pyrite - from the mining of pyrite ores to give sulphides 3. Sulphur-in-other-forms - this type may come from a number of sources, among them (a) Waste gases from zinc, copper, lead or nickel smelters (b) Gypsum or anhydrite (c) Hydrogen sulphide content of oil refinery or coke oven gases (d)—Oilrefinery acid sludge Phosphoric acid Phosphoric acid is produced by oxidizing red phosphorus with nitric acid or whit phosphorus under the surface of water with bromine or iodine. It is also obtained by decomposing a mineral phosphate with sulphuric acid Phosphoric acid has a wide variety of uses, probably the most important of which is its use as a reactant with ground rock phosphate to produce high-grade super phosphate, a much-used fertilizer. Phosphoric acid is also used as an intermediate for the production of various phosphates which in turn are used for rust proofing, the manufacture of foodstuffs, for water softening, synthetic detergents, emulsion paints, fireproof materials and pharmaceuticals. Demand for phosphoric acid increased rapidly up until 1973 because of the wide variety of products which could be derived from it, particularly fertilizers. Phosphoric acid is produced from the reaction between phosphate rock and sulphuric acid. The major sources of phosphate rock are North African phosphate prices increased dramatically and for the first time it became economic for European fertilizer manufacturers to buy North African produced phosphoric acid. North African acid production capacities growing and although European phosphoric acid manufacture is still viable itis unlikely that any further capacity will be built. Nitric acid Pure nitric acid is a colourless liquid which fumes and is unstable. Commercial grades of nitric acid are approximately 68 % and 94 % concentrations. Because of its instability even dilute nitric acid gives off oxygen and is therefore a strong oxidising agent, Miscopll AS, Transportation of Chemicls in BulkNitric acid is produced today principally by the Ostwald Process which involves the oxidation of ammonia and requires as basic raw materials, coal, water and air. Nitric acid’s basic uses include: 1. Manufacture of practically all explosives. Many of the derivatives obtained from nitric acid are explosives, nitro-glycerin being one example 2. Many nitrates are obtained from nitric acid, most of which are used as fertilizers, 3. Nitric and is also used in the manufacture of dyes, plastics and lacquers. Caustic soda Caustic soda or lye is known chemically as sodium hydroxide. It is called caustic soda because of its buming or caustic effect on the skin. It is one of the basic raw materials of the great alkali industry which, in itself, is one of the most important parts of the chemical industry. Caustic soda is produced commercially in either of two ways, the electrolysis of brine or the Soda-Lime Process. Pure caustic soda is a white solid that is very soluble in water. It is deliquescent, absorbing water from the air and dissolving in it. In this way it is carried in bulk as a 50 % or 70 % solution; it is known as caustic soda liquor and is a colorless or grey, syrupy liquid with a slight characteristic odor. Caustic soda is a caustic alkali (strong base) which attacks and decomposes organic matter. It dissolves wool and silk and eventually reacts with cellulose to form a compound from which viscous rayon is manufactured. It reacts with fats to form soap, dissolving fat and grease. Other uses of caustic soda are: 1. Removal and solution of waste in plumbing. As household lye, caustic soda is poured down clogged drains where it liquefies or dissolves waste fat and grease, making them soluble in water. 2. Petroleum purification. Caustic soda is used to neutralize the sulphuric acid employed in purifying petroleum. 3. Manufacture of mercerized cotton. Cotton cloth when treated under tension in a solution of caustic soda becomes stronger and more lustrous. Cotton treated in this manner is known as mercerized cotton. 4. Vegetable oil refining and aluminum process. 5. Reclaiming rubber, etching and electroplating, Ammonia Ammonia is synthesised from nitrogen and hydrogen by the Haber process. The first commercial plant was built about sixty years ago on the Rhine and produced 30 tons/day but plants are now being built of 1500 tons/day using high pressure and Miscopll AS, Transportation of Chemicls in Bulk 2stemperature. In the USA almost all of the hydrogen required is obtained from natural gas (Methane) whereas in the UK it is from natural gas and naphtha. The average increase in consumption during the early and mid 70s was 7.0 % but this has declined now to about 5.4 %. Ammonia is probably the largest volume industrial chemical manufactured in the western world but it is mainly transported as gas (anhydrous ammonia) nowadays and so is not of direct interest to this report. Aqueous ammonia, that is the gas dissolved in water, is an IMO cargo that is sometimes carried within the S.e Asia, Japan and Australia region. Miscopll AS, Transportation of Chemicls in Bulk 2ee Chapter 2 CHEMISTRY AND PHYSICS Transportation of Chemicals in Bulk (Tankerman Highest Grade) Department/Author: Approved by: Kjell Vagtberg Erik Frette Seagull ‘Seagull 20007 SEAGULL AS All rights reserved No part of this work covered by the copyright hereon may be reproduced or otherwise copied without prior written permission of SEAGULL AS GaDOCUMENT STATUS Flo K'5-Training\St-Menvoler og underlg\Tankor Operation - Chamicals'Revsion 200701 Advanced Choma! Issue No. | Date/Year | _ Inc. by Issue No. | Date/Year | _ Inc. by 14278 | 08. June kv o7 ‘CHANGES IN DOCUMENT Issue Paragraph Paragraph Heading No. No. Description of Change B Updated in accordance with new regulations. Segal 4S Transportation of Chemis ule ATABLE OF CONTENTS Section Page CHEMISTRY AND PHYSICS. 2 2.1 PHYSICAL PROPERTIES OF CARGO 2.1.1 Aggregate states . 21.2 Solid Substances. 213 FUIDS cessor 214 Gases 21.5 Phase changes. 21.6 MELTING 21.7 Enthalpy 2.1.8 Evaporation 2.1.9 Boiling. 2.1.10 Condensation 2.1.11 Distillation eoron : . 2.1.12 Saturated and unsaturated or superheated steam 2.2 CHEMISTRY OF CARGO 2.2.1 The periodic system 2.2.2 Carbon 2.3 HypRo CARBON GROUPS 23.1 Alkanes. 23.2 Alkyls... 23.3 Alkenes..... 23.4 Alkadienes 23.5 Alkynes. 2.3.6 Cyclo alkanes: 23.7 Arenes. 2.3.8 Alcohols 2.3.9 Aldehydes. 2.3.10 Ketones..... 2.3.11 Acids and Base: esse : 2.4 — CHEMICAL BULK LiauiD CARGOES 16 CNOOADAAGONNNAGSS Oo 2.5 CHEMICAL REACTIONS 7 2.5.1 Peroxides and inhibitors 19 2.5.2 Reaction with other cargo and materials 20 2.6 ‘TRUE vaPouR PRESSURE (TVP) 20 2.7 THE REID VAPOUR PRESSURE (RVP). 20 2.8 FLASH POINT... . 24 For further information please see CBT # 0032 Liquid Cargo Properties and CBT # 0096 Cargo Compatibility Segal 4S Trarsportation of Chemo Bult uw2. CHEMISTRY AND PHYSICS 2.1 PHYSICAL PROPERTIES OF CARGO The personnel (crew) operating the ships provide a wide range of knowledge regarding ship operations and its specific cargo. To be an educated and qualified "Ship Officer’, it is necessary to have a basic theoretical knowledge and a lot of practical experience on board the ships. In this part of the compendium, the chemical's physical properties are reviewed. Physics is the learning of different substances and property forces and their energy form. Chemistry is the learning of the substance’s composition and the substantial or permanent changes these substances may under go. The theory about atoms and molecules understands that substances are able to divide into smaller parts, atoms and molecules. 2.4.1 AGGREGATE STATES Solid, fluid and gas form conditions must be seen in connection with the understanding of molecule forces. An example: When splitting a piece of wood the molecules separate along the split area. The force being used corresponds with the force binding the molecules together. If you now wish to force the two pieces together again, a certain power has to be used The first power in use will be called the force of cohesion. The second power in use will be called the force of expansion. Cohesion and expansion summed, is called intermolecular force. The cohesion is due to the fact that all substances (elements), including the smallest parts in a substance, executes a mutual back sweep on each other. We therefore have the same nature as the force of gravity. It decreases rapidly when the distance between the smallest parts increases. The expansion is due to the fact that the molecules in all substances, both solid, fluid and gas forms execute movements or vibrations and therefore fill-up an entire room. 2.4.2 Sotip SuBstances A solid substance has a fixed form and fixed volume. An iron bar resists being lengthened or pressed together. The molecules in the iron bar will try hard to keep a certain mutual distance to each other. The iron bar is resistant to rubbing and bending. In solid substances the molecules have fixed places according to each other, and the same applies to the substance’s volume and form. This is because the cohesion and expansive force is very large. 2.4.3 Fiuws Fluids have a fixed volume, but do not have any fixed form. To squeeze water in a cylinder with tight-fitting piston is hard without using large power. Similar to the molecules in solid substances, the molecules in a liquid substance have a certain mutual distance between each other. The liquid molecules on the other hand have no fixed positions according to each other. Liquid will always be shaped based on where the liquid is stored. The cohesion force in liquids is not powerful enough to prevent the molecules from moving freely according to each other. However, the force is still strong enough to maintain the Ba Scapa 45, Troportaionof Choma i Bulk 1distance between each of the fixed molecules. The expansion force is equal as in solid substances. 2.1.4 Gases Gases have no fixed volume or fixed form. A gas will always try to fill as great a volume as possible, and will therefore fill the room, the tank and so on, where the gas is stored. The cohesion force in gas is too small to prevent the molecules from changing both the distance and the position in accordance with each other. The expansion force gets free scope and the gas expansion is total and unlimited. By exposing gas to forces greater than the expansive force it, the gas will be compressed. 2.1.5 PHASE CHANGES ‘Any substance can be transformed from one condition to another, by means of temperature changes or varying temperatures and pressure. Ice, water and water vapour are the same substance in different forms. The transformation between cohesion and expansion with water molecules goes through these three phases - solid substances, liquids and gases. Pressure 2.4.6 MELTING When a solid, pure crystal substance is continuously supplied with heat, the substance will melt. For example: 1 kg of ice with a temperature of minus 20 degrees Celsius exposed to heat (the pressure is 1 atm). A thermometer placed in the ice will show a rise in temperature up to 0 degrees Celsius, which is melting point of the ice. The heat supplied after the meting point is achieved will have no effect to any temperature rising, as long as the ice is present.During the melting, the temperature is invariable, and the heat supplied during the melting process is consumed in melting the ice. When all the ice is melted, the temperature in the water will rise. So, the amount of heat supplied to 1 kg of the solid substance, in order to reach the melting point where the change from solid to liquid form occurs, is called the *metting heat’. The heat needed to transform a solid substance at a given temperature, into a liquid substance with the same temperature, is called the “specific melting heat’. The unit for specific melting heat is Joule/kg. The heat necessary to evaporate one Kilo of a certain liquid substance is called “specific melting heat’, abbreviated “r’. The unit for specific evaporation heat is J/k. © om EAE 2.4.7 ENTHALPY A substance's total energy consists of the extemal energy (work) plus the internal energy. Enthalpy is an expression for a substance's internal energy abbreviated “h’. This enthalpy is an expression of how much energy is tied up in one kilo of the substance. The unit for enthalpy is Joule/kg. The comparison of enthalpy to temperature change of gradients shows how much energy is needed to be supplied to bring ice through the three different stages. 2.1.8 EVAPORATION When a liquid change to gas is called evaporation. This. may happen by fH evaporation or boiling. To achieve evaporation, heat of evaporation is needed. Some liquids evaporate very quickly, such as gasoline and ether. Other liquid substances evaporate very slowly, such as in crude oil. Evaporation is vapour formed out of the liquid surface and occurs at all temperatures. This is explained by some of the liquid’s surface molecules being sent into the air, which is strongest at high temperatures, dry air and fresh wind.The specific temperature calls the amount of heat needed for one Kilo of liquid with fixed temperature to form into one kilo of steam with the same temperature” The heat from evaporation is set free when the steam forms to liquid again, or condenses The heat necessary to evaporate one kilo of a certain liquid is called “specific heat of evaporation’, abbreviated as (r). The unit for specific heat of evaporation is J/kg. 2.1.9 BoIine Boiling is steam formed internally in the liquid. The boiling ocours at a certain temperature, called "the boiling point’. Water is heated in normal atmospheric pressure (1 atm), in an open container. In common, some parts of air are always dissolved. The rise in temperature is read from a thermometer placed in the liquid’s surface. When the temperature has reached 100 degrees Celsius, steam bubbles will form inside the liquid substance, especially in the bottom of the container. With continuous heat supply, the bubbling will rise like a stream towards the surface and further up into the air. The water is boiling. The formation of bubbling steam can be explained as follows: During the heating, the water molecule's kinetic energy increases, consequently the molecules demand more space. During the boiling, as long as there is in water in the container, the temperature will be 100 degrees C. The boiling point is dependent upon the pressure. If the steam or the atmospheric pressure increases above liquid substance, the boiling point will also rise. If the surface temperature is just below the boiling temperature, then the water steam will evaporate on the surface. The evaporation point and the boiling point will be the same accordingly. The pressure from the surrounding liquid is the total amount of pressure above the liquid, Pa, plus the static liquid pressure. P =pa +(pxgxh) Pe P= pressure in Pascal (100 000 Pa + 1 bar) pa= barometer pressure p= the liquid density in kg/m* g force of gravity acceleration (9,81m/s?) h = liquid column in meter. When reducing the pressure above the liquid, the boiling point will also be P=p,*(Pxgxh) reduced. A practical use of this po characteristic is the production of fresh water on board (fresh water generator). 2.1.10 CONDENSATION Condensation is the opposite of evaporation. If a gas is to be changed to liquid at the same temperature, we must remove the heat of evaporation from the gas. A gas can be condensed at all temperatures below the critical temperature. By cooling a gas, the molecule speed decreases hence the kinetic speed. The internal energy decreases, as well as, the molecule units and liquid forms. Ba Scapa 45, Troportaionof Choma i Bulk 42.4.11 DISTILLATION Distillation is a transferring of liquid to vapour, hence the following condensing of vapour to liquid. Substances, which were dissolved in the liquid, will remain as solid substance. With distillation it is possible to separate what has been dissolved from the substance which was being dissolved. When a mixture of two liquids with different boiling point is heated, will the most volatile liquid evaporate first while the remaining becomes richer on the less volatile. On board, for instance, seawater is distillate by use of an evaporator. 2.1.12 SATURATED AND UNSATURATED OR SUPERHEATED STEAM Let us imagine boiling water, releasing vapour from a container, and leading the steam into a cylinder that is equipped with a tightening piston, a manometer and two valves. The steam flows through the cylinder and passes the valves, whereon the valves are closing. There now is a limited and fixed volume of steam in the cylinder. Around this cylinder a heating element is fitted. Vapour from the container is constantly sent through this heating element to ensure that the temperature is maintained constant. The piston is pressed inwards, and now the manometer should show a rise in pressure. But, the manometer shows an unchanged pressure regardless how much the volume is reduced. What's happening is, the further the piston is pressed inwards, some parts of the steam is condensed more, and using less volume. The vapour from the heating element removes the condensed heat, which is liberated during the condensation process. We find that the amount of steam, which is possible to contain per volume unit, remains constant when the steam’s temperature is equal to the condensation point at the set pressure. The room cannot absorb more vapour, it is salurated with steam and called "saturated’. If the piston is pressed outwards, the pressure will still show constant. The conclusion is: With temperature equal to the condensation point by set pressure, steam is saturated, Steam above boiling water is saturated. Saturated steam with a set temperature has a set pressure. This is called saturation pressure. ‘With constant temperature saturated steam cannot be compressed This also concerns vapour as saturated steam of other gases. Using the same cylinder arrangement as before. The cylinder contains saturated steam, no water. The piston is drawn outward. When no water exists over the piston no new steam will be supplied underneath. The manometer will now show reduced (falling) pressure as the steam expands. When saturated steam expands without supplying new steam, it is called unsaturated steam. The room has capacity to collect more steam. So: Unsaturated steam contains lower pressure than saturated steam at the same temperature. The unsaturated steam in the cylinder can be made saturated again in two ways. Either by pushing the piston inward to the originated position, or let the unsaturated steam be sufficiently cooled down. When the temperature is reduced, the saturation pressure will reduce. Unsaturated steam will, in other words, have a Ba Scapa 45, Troportaionof Choma i Bulk 5too high temperature to be saturated with the temperature it originally had. ‘Therefore, this often is referred to as superheated steam. 2.2 CHEMISTRY OF CARGO Organic chemistry mostly deals with chemical compounds containing carbon. 2.2.1 THE PERIODIC SYSTEM ‘The periodic system is built on the principle that the electrons in the outer shell determine the chemical Properties of a material. An atom consists of protons, neutrons and electrons. Protons and electrons form the atomic nucleus. The electrons move with high velocity around the nucleus, at different levels and orbital. The levels are numbered from K to Q and called electron shells. At maximum, there can be 8 electrons in the outer shell. There are equal numbers of protons as electrons in an atom, meanwhile the number of neutrons may vary. ‘The periodic table arranges the 106 elements in increasing number of electron shells. Each vertical column is one of the periodic table's main groups. The number of electrons in the outer shell is always equal to the atom’s main group number. Two of the main elements in the periodic system are Hydrogen and Helium, and fall under group IA and VIIA. The atomic models are illustrated as follows: Carbon falls under group IV A and has 4 electrons in the outer shell © Hekxon ® voycon ® Proton The elements in the group IA have only one electron in the outer shell. It is therefore easy to emit one electron to elements within group VIIA, which has seven electrons in the outer shell and is “short of’ one electron to fill up the outer shell. Such mutual sharing of an electron is called ion bonding. An example for such a bonding is when Sodium (Na) and Chlorine (Cl) bond with one another and form Sodium chloride or cooking salt. Na+Cl Na’ + Cr Nacl Sodium “emits” the only electron to Chlorine, and is thereby positively charged. ©©-©©0 Ba sepa 45 Travopotationof Chania Bulk ‘Chlorine “receives” the electron and is thereby negatively charged. Wee call this mutual sharing of electrons, covalent bonding. Covalent bonding is common in both organic and inorganic chemical reactions. When two or more atoms bond together, they form a molecule. There are 8 side groups between the main groups IA and IIA. All the elements in the side groups are metals, and they easily form alloys with one another. The rows in the periodic chart indicate the periods. The 7 periods indicate the humber of electron shells. Sulphur is located in row 3 (period number 3) and has thereby 3 shells. We also look at the electron shells as the electrons’ energy level. The elements in group VIIA are named noble gases. Noble gases occur only in atomic form. Most inorganic elements are metals. The metals form metal bonding where the atomic are organised close together. The individual element has numbers from 1 to 106, The periodic system's number is the element's atomic number. The atomic number also indicates the total number of electrons in the atom. Atorsie number Symbot Name Atomie weight 2.2.2 CARBON You find the element Carbon in the main group IVAJperiod number 2, which has four electrons in the outer shell number 2, The atomic number for carbon is 6, which means there are totally 6 electrons divided between two electron shells with 4 electrons in the outer shell, and 2 electrons in the innermost. There are many isotopes of carbon. Isotopes have the same number of protons, but different number of neutron in the atomic nucleus. There are two natural forms of Carbon, graphite and diamond. Carbon is not particular reactive in room temperature. When heated, it will easily react with for example, Oxygen. We say that carbon is combustible. The different products of the combustion are dependent of accent to oxygen. C+, = CO,+393kJ (at complete combustion) C +050, O+113kJ (at incomplete combustion) Both reactions are exothermic, that means heat is produced in the chemical reaction. Both reaction products are also gases. Carbon dioxide, COz, is the product of complete combustion of carbon and carbon monoxide, CO, which is the product of incomplete combustion of carbon A partly incomplete combustion produces both less heat and more formation of carbon monoxide than a complete combustion. Carbon monoxide is odourless and a Ba Scapa 45, Troportaionof Choma i Bulk 1very poisonous gas that always is present in a real combustion process. Inert gas produced in an inert gas generator or flue gas plant onboard will always contain carbon monoxide due to incomplete combustion, especially when the air excess is reduced Poisoning of carbon monoxide occurs because the haemoglobin in the blood reacts much easier with CO than with oxygen. When you breathe a mixture of these two gases, CO is thereby first absorbed in the blood and seizes the absorption of oxygen. The result of this poisoning is a sort of suffocation at very low concentrations. These relations are very important to notice. You must always check the cargo tank atmosphere for carbon monoxide before personnel are allowed to enter the tank. Group= 123 4 5 6 7 8 9 10 11 12 13 14 45 16 17 18 I Period 2 : i a 2 Tiled 12 3 IM 20) 4 cal 5 38 47 | 48 [49 2 sr WenllechAgl ca in 56 ere Pb 66] 67 | 68 [69] 70 Tb || Dyl] Ho tu2.3. HYDRO CARBON GROUPS Hydrocarbon is a common expression for all chemical compounds that includes carbon and hydrogen. Hydrocarbons with from five to twenty carbon atoms are liquid at ambient conditions. Hydrocarbons with more than twenty carbon atoms in their molecules are solid at ambient conditions. You find the element carbon in only two different natural conditions, as graphite and as diamond. Carbon is the element that naturally forms most natural chemical compounds. It is not reactive in room temperature, but it will when heated up react more easily with, for example, the oxygen in air. We say that the carbon is combustible. The combustion is exothermic, which is a reaction that produces heat. Hydrogen is the smallest main element. The gas (H.), is light and is flammable in air. There are small quantities of hydrogen in free natural form on earth. Hydrogen is strongly widespread, first of all in form of water and naturally compounds together with carbon. Crude oil and natural gas consist mainly of a mixture with various unequal hydrocarbon compounds. Following sketch indicates an example of a natural gas’ composition: Ba Scapa 45, Troportaionof Choma i Bulk °Natural Hydro- Gas carbons from Heavy Naphta fractions, Natural gasoline and wells min 5 other, C5 + C-atoms Non- hydro- carbons Water, carbon dioxide etc. Carbon has four electrons in the outer electron shell that can be divided with others. You may look at the four electrons as four “arms” that can connect to the hydrogen atom’s single “arm”, and creates hydrocarbon compounds. ‘Some of the hydrocarbon compounds are naturally created; other are only created in chemical controlled processes. To simplify the overview of these natural components, and all new hydrocarbon compounds that is created in the petrochemical industry, the different hydrocarbon compounds are grouped dependent of how the “arms” or the chemical bonding are between the two atoms. The most important hydrocarbon groups are: Alkanes, also called Paraffin’s Alkyls Alkenes, also called Olefins Alkynes, also called Acetylides Alkadienes, also called Di-olefins Cyclo-alkanes Arenes Alcohol Aldehyds Ketones In addition to above listed hydrocarbon groups there are others like Carboxylic aci Esters, Ethers etc.2.3.1 ALKANES Alkanes are the simplest hydrocarbon compounds and is the major part of crude oil and natural gas. The carbon atom's four arms are united to the hydrogen atoms’ single arm and has this general molecule-formula C,Han+2 where "n” is a positive integer. All alkane compounds have the ending *-ane. The gas methane is the smallest molecule, and is the main component in natural gas. A methane molecule consists of one carbon atom and four hydrogen atoms By adding one carbon atom and two hydrogen atoms to methane, we get ethane, which is the next component in this group. By adding carbon atoms and hydrogen atoms, and at the same time maintain the same simple form of binding, new alkanes are formed. The third component in the alkane group is propane, C3Hs. When the number of carbon atoms increase, the number of possible bonding between the atoms increase. You can arrange 20 carbon atoms and 42 hydrogen atoms in 366319 different ways. + de He Methane Ethane Propane Many materials may have the same molecule formula, but the properties (boiling point, density, etc.) are different because the atom structure is different Such bonding is called isometric bonding. Normal-butane and iso-butane are examples of isomers where both have the same molecule formula, but different properties. n-Butane, CaHio iso-Butane, CsHio Ba Scapa 45, Troportaionof Choma i Bulk wChemical formulas and names are many times derived from each other. Pentane is derived from the Greek word “pent’. That means “five’, it refers to the number of carbon atoms in the material. Other names like methane and ethane are not following this system. These names are called trivial names. In the following list, some of the most common alkanes are listed with melting- and boiling point at atmospheric pressure. Note that melting point and boiling point increase by the length of chain for the straight-chained hydrocarbons. Melting | Boiling | Number of Name: Formula | point point isomeric ec °c | compounds Methane CHs -182,5, -161,6 oO Ethane CoH 183.2 | 886 ° Propane CoHs 1899 | 425 0 n-Butane Catto “135 05 2 iso-Butane | CeHio “145 117 n-Pentane CsHi2 -130 36 3 nmHexane | Cote 95 69 5 mHeptane | CrHis ca 98 n-Octane Cotte 57 126 18 nNonane | CoHoo 54 151 35 n-Decane CroHze -30 174 75 2.3.2 ALKYLS If one hydrogen atom is removed from an alkane molecule, an alkyl molecule is created. The different compounds are named by the alkane, but with the ending "-yl instead of "-ane”. The general molecule formula for alkyl groups are: CoHzn + 1 ‘The compounds in this group are chemical products where the CH-group is attached to various alcohol and chloride compounds. 2.3.3 ALKENES You do not find alkenes in the natural forms. These compounds are produced in a cracking process within the petrochemical industry. Alkenes are hydrocarbons with a double bonding between two of the carbon atoms. The general molecule formula for alkanes is:CyHen The simplest alkene is ethylene, C2H., that is produced by cracking of for example propane, ethane, butane or naphtha. The next alkene is propylene, C3H6, which is produced by cracking other hydrocarbons or naphtha. The alkenes are so-called unsaturated hydrocarbons. The double bonding may easily loosen up, “arms” that are attached to several hydrogen atoms released, and the alkenes may change back to (chemical reaction) alkenes. Melting Boling [Number of Name: Formula point point _ isomeric fa Ey compounds Ethylene CoHs =169—-(|-103,7 [0 (ethene) Propylene CoH 1852 |-47.7 Jo (propene) CuHs 1854/63 4 CuHs -138,9 |3,7 4 CiHs 105.6 |0,9 4 iso-Butene CiHe 1404 |-6,9 4 4-Pentene CoHyo 6 ‘The number of isomeric compounds increase by the number of carbon atoms. Double bonding also gives additional possibilities for combination because the double bonding may be located on several different places inside the molecule. The following molecules have the same molecule formula, but different structure and thereby different properties. Notice the difference between a cis-bonding and a trans-bonding. 9 1-Butene cls Cis-2-Butene H 3 ” Trans-2-Butene 5 { Ba Scapa 45, Troportaionof Choma i Bulk 12.3.4 ALKADIENES Alkadienes are hydrocarbons with two doubles bonding in the molecule. The general molecule formula for Alkadienes is: CyHon-2 ° Propadiene ° 1,3-Butadiene 9 3 Number of Name: | Formula isomeric compounds Propadiene _|G:Hs 0 4,3- Cis Butadiene 2.3.5 ALKYNES Alkynes are hydrocarbons with a triple bonding between two carbon molecules. The alkynes have the same general formula as for the alkadienes: CrHon—2 0 ‘Alkynes are unsaturated hydrocarbons, and form a homologous serial. The simplest compound within this group is etyne, CoHz Melting [Boling [Number off Name: Formula | point point isomeric °C kc compounds, Etyne CH -82 “84 0 (Acetylene) Propyne CoH -102 -23 0 (Allyene)2.3.6 CYCLO ALKANES Cyclo alkanes are hydrocarbons with single bonding between the carbon atoms, but the molecules form a circular structure. The compounds are saturated, and form a homologous serial. The general molecule formula for the cyclo alkanes is; CaHen The circular structure of the cyclo propane: Melting |Boiling | Number of Name: Formula | point point isomeric °C °C. compounds. Cyclopropane | C3He 126 -34 Cyclobutane |C.Hs -60 8 Cyclopentane | CsHio -93 50 Cycloheptane | CsHiz 6 at 2.3.7 ARENES Arenes are cyclic, but unsaturated hydrocarbons because of its double bonding. The compounds are aromatic. Benzene, which is very stabile and frequently used together with other products in the petrochemical industry, is a well-known product within this group. Melting [Boiling [Number of] Name: Formula | point point isomeric °c 8 compounds Benzene CoH. 55, 80,1 2.3.8 ALcoHoLs Alcohols are organic compounds where the functional group is the hydroxyl-group — OH. All alcohol ends with "ol". The different alcohols are divided in subgroups, dependent of the form of bonding, of Name: Formula ec} °c compound, Methanol [CH,OH —_|-97,8 64,5 Ethanol CoHeOH _|-117,3 [78,32.3.9 ALDEHYDES Aldehydes have one functional group -CHO. Melting |Boiling _|Number __of| Nam Formula |point | point isomeric ‘ce °c compound Formaldehyd [HCHO |-118 19 e Acetaldehyde |CHsCOH |-123,5 _|20,2 2.3.10 KETONES Ketones are compounds where the functional group is the carbon-group. Melting |Boiling )Number of Nam Formula | point point isomeric ec} °c compound, [Acetone CH;COCH; |-94,3 56,2 2.3.11 Acips AND Bases ‘An acid is any substance which liberates hydrogeneions or causes an increase in the concentration of hydrogenous. With the base it is the opposite. Their ability to absorb or neutralize H" is great for the strong bases, but not so great for the weak bases. A strong acid as well as strong bases are almost 100% dissociated into ions into watery solutions. All this reactions are equilibria and can be denoted by an equilibrium constant, Ka. For both acids and bases the H' concentration is given by the pH value. 24 CHEMICAL BULK LIQUID CARGOES During the 19th and early 20th century, the manufacture of synthetic organic chemicals depended principally on the raw materials such as coal, limestone, cellulose and molasses. However, with the development of the infant petroleum industry attention was focused upon this new base which was rapidly identified as a convenient, cheap plentiful and rich source of the intermediates required for the production of useful chemicals. The early chemical industry was thus linked closely to the fortunes of the petroleum business and the first petrochemical plants were to be found in the United States adjacent to the first oil refineries. From its beginnings in the 1920s, the new industry enjoyed success from the outset with a rapidly increasing demand for new substances such as plastics and synthetic rubbers. The crisis and shortages of the Second World War gave further impetus to the young petrochemical industry as demand for its product soared. In the years since, the constant identification of new products and the gradual growth of chemically produced substitutes for a vast number of products.By the 1960s, when the significant carriage of its products by sea in bulk began the chemical industry had become a major contributor to all the important facets of modem life, its products playing a significant role in food, shelter, transportation, health and communication. The chemical industry's lists of product reaches into every endeavour from the most basic of agriculture and fertilizers, synthetic fibres and rubbers in addition to the materials used to package these important commodities. Chemicals have, in fact, provided the basis of a whole new group of new industries themselves, in a procteative development deriving from its own improved technologies. The increasing demand for chemical products throughout the world has led to the development of sophisticated seagoing vessels capable of carrying a wide range of special cargoes in bulk. All these cargoes belong to one of the following family groups of chemicals: Acids-organic Glycols Acids-inorganic Glycol-ethers Alcohols Halogenated compounds Aldehydes Halogens Alkalis, Hydrocarbons ‘Amines Ketones Esters Nitriles Ethers Phenols However in general terms, shipments in chemical tankers usually take the form of solvents, aromatics, intermediates or refined products. Chemical tankers do carry a variety of products which aromatics, intermediates or refined products. Chemical tankers do carry a variety of products which would normally be considered to be unrelated to chemicals, ie. wine, molasses, animal and vegetable oils. However, these cargoes belong to one of the above listed chemical family groups and require as much care and attention as many “chemical” cargoes. For this purpose, chemical tankers cargoes will be considered to belong to one of the following groups: Petrochemical products Coal tar products Molasses and alcohols Vegetable oils and animal fats Heavy chemicals (inorganic substances) Having thus briefly introduced the chemical industry, we will now examine each of these cargo classifications and the principal cargoes within each category. 2.5 CHEMICAL REACTIONS New products are continuously made in the petrochemical industry by allowing hydrocarbon compounds participate in chemical processes and reactions. Unsaturated chemical compounds contain one or several double or triple bonding between the carbon atoms. They can easily saturate the vacant valences in a chemical reaction, Ba Scapa 45, Troportaionof Choma i Bulk ryA chemical reaction may take place: by mixing unsaturated compounds with another product. by increasing the temperature and pressure in the chemical compound, alone or together with other compounds. To visualise an unsaturated compound, a solvent bromine and water can be used. If you mix bromine (Br) with a saturated oil, the bromine-coloured water will disappear, because the double bonding is opened and bromine appears in every vacant valence. A chemical reaction has appeared between two compounds, and a new compound is created. Ifyou combine ethylene and bromine, this chemical reaction will take place: @ @ @ @ ©=0 + Br, @-©-O-@ ® @ ® © When unsaturated chemical compounds are heated under pressure, the molecules react with each other and form large molecules, so-called macromolecules. This is called polymerisation. To start the reactions or to increase the velocity of reaction, a catalyst is often used. A catalyst is a material that increases the velocity of reaction in a chemical process without changing its own state. Linear polyethylene is a plastic raw material, which is a polymer of ethylene produced by polymerizing ethylene with a peroxide catalyst. Benzol peroxide is an example of peroxide used as a catalyst for production of polyethylene. Other types of polymers are made of ethylene or together with other hydrocarbon. The properties are different, and the plastic raw materials are used alone or together with others when producing plastic products, Most plastic raw materials are produced like this. Molecules or mixture of molecules, which is capable of, polymerize, are called monomers. The number of monomers taking part of a polymerization may be many thousand. A linear polyethylene has a molecular weight of more than 6000, others are considerably smaller. The molecular weight is controlled by temperature, concentration of catalyst or amount of ethylene. It is not only the unsaturated hydrocarbon compound that may polymerise. In 1907, Baekeland managed to control three-step polymerising with phenol and formaldehyde. The product “Bakelite” was the first synthetic polymer that was produced, and has great significance even today. Ba Scapa 45, Troportaionof Choma i Bulk 18The following list demonstrates some of the most common plastic materials today, and how they are produced Polymer ‘Monomer Polymerisation: Polyethylene (CH). Ethylene Polytetrafluorethylene | (C2F)n Tetrafluorethylene (PTFE) Polyvinylcloride (H.CCHF), Vinylcloride (PVC) Polypropylene (C3Hs)a Propylene’ Polystyrene. (CsHsCHCH2)> Styrene monomer 2.5.1 PEROXIDES AND INHIBITORS Peroxides are highly explosive, and can form into unsaturated compounds, as for example butadiene and VCM if oxygen is present. They can appear as powder in pipes and tanks and are very unstable and can easily explode. The formation of peroxides in butadiene can entail polymerizing with powerful heat generation. To avoid such a chemical reaction, the content of oxygen in the tank atmosphere is kept as low as possible. To assure that all oxygen is removed, an inhibitor is added to the individual cargo. An inhibitor is a material that itself, in low concentrations, reacts with the oxygen. Some types of inhibitors have the capability to react with radicals so that the velocity of reaction reduces or to cease up. Most inhibitors are very dangerous to our health, and must therefore, be handled with the utmost care. Butadiene and VCM are examples of cargo that are added inhibitors. Approximately 5 ppm hydroquinon is added to VCM to prevent polymerisation. US Coast Guard requires that one add 100 ppm TBC (Tertiary Butyl Catechol) to 1,3 butadiene to prevent a polymerisation with strong heat generation. Humidity and water will reduce the effect of inhibitors, in some cases water will accelerate a chemical reaction. Cargo that is inhibited, must have a certificate with: * name and amount inhibitor date and for how long the inhibitor is efficient precautions, if the voyage lasts longer than the effect of the inhibitor eventual temperature limitation The above mentioned inhibitors are only present in the liquid phase. In all probability, dangerous peroxides will be formed inside the lines of the cooling plant's “condensate” system. It is recommended that these parts of the system are checked regularly, when the inhibited cargo is cooled. Further, it is recommended to circulate some inhibited liquid through the part of the system where “condensates” remains without the inhibitor. Introductorily, we have said that polymerizing can occur if the temperature is high enough. The following restriction of maximum outlet temperatures from the compressor are required maximum 60 °C for butadiene maximum 90 °C for VOM2.5.2 REACTION WITH OTHER CARGO AND MATERIALS Some cargo can react strongly with other cargo. This makes great demands for cleaning, before loading and full segregation against other cargo. Whenever cargo segregation is required, spool pieces must be used. It is important that all materials are compatible with which the cargo can come in contact. The material must, for example, in all gaskets that can be in contact with propylene oxide be of PTFE or a similar approved material type. 2.6 TRUE VAPOUR PRESSURE (TVP) Most usual petroleum products are essentially mixtures of a wide range of hydrocarbon compounds. The boiling points of the compounds range from -162°C (methane) to well in excess of +400°C, and the volatility of any particular mixture of compounds depends primarily on the quantities of the more volatile elements. The volatility is characterized by the vapour pressure. When transferring a petroleum product to a gas-free tank it begins to vaporize, that is, it liberates gas into the space above it. This gas has also a tendency to re-dissolve in the liquid. The pressure exerted by this gas is called the equilibrium pressure of the liquid, usually referred to simply as the vapour pressure. The vapour pressure of a pure compound depends only upon its temperature. With a mixture of compounds, the vapour pressure depends on the temperature, elements and the volume of the gas space in which vaporization occurs. The true vapour pressure (TVP) or bubble point vapour pressure is the equilibrium of vapour pressure of a mixture when the gas/liquid ratio is effectively zeroed. The highest vapour pressure that is possible at any specified temperature. As the temperature of a petroleum mixture increases, its TVP also increases. If the TVP exceeds atmospheric pressure, the liquid begins to boil. The TVP of a petroleum mixture gives a good indication of its ability to give rise to gas, but unfortunately it is a property which stil is extremely difficult to measure. 2.7 THE REID VAPOUR PRESSURE (RVP) Testing is a simple and generally used method for measuring the volatility of petroleum liquids. Measurement of the RVP is conducted at 37,8°C (100°F). The greater the RVP value, the more volatile is the oil. Normally crude oil has a RVP of between 0,1 and 0,8kg/cm’. ‘A sample of liquid is put into the test container at atmospheric pressure. The volume of liquid should be one fifth of the container's total volume. Then the container is sealed and immersed in a water bath, which is heated to 37,8°C. The container is then shaken in order to mix the liquid properly and the rise in pressure due to vaporization can be read on the attached pressure gauge. This pressure gauge gives a close approximation in bars. Because the liquid’s vapour pressure is at 37,8°C, RVP is useful for generally comparing the volatility of a wide range of petroleum liquids. However, it has, small value as a means of estimating the likeliness of gas evolution in specific situations, mainly because the measurement is made at the standard temperature of 37,8°C Ba Scapa 45, Troportaionof Choma i Bulk 20and at a fixed gasiliquid ratio. For this purpose TVP is much more useful. As mentioned, in some cases, correlation exist between TVP, RVP and temperature. For safety measures against fire on ships, SOLAS uses 61°C as limit value for flash point and 2,8kg/cm? for vapour pressure at 37,8°C. The oil referred to in this regulation is: Mineral oils with a flash point below 61°C, such as kerosene, benzene, gasoline and crude oil or other flammable liquids with a flash point below said limit. Mineral oils with a flash point of 61°C or higher, such as marine gas oils, fuel oil, diese! oil, lubricating oil, which give off flammable gases when heated. Oils and fats of animal or vegetable origins, such as whale oil, groundnut oil, inseed oil etc., which give off flammable gases when heated, The liquid chemicals referred to are: Chemicals with an absolute vapour pressure lower than 2,8kg/cm? at 37,8°C. ‘The condensed gases referred to are: Chemicals with an absolute vapour pressure of 2,8kg/cm? or higher at 37,80C. 2.8 FLASH POINT The flash point for hydrocarbon liquid is the temperature at which it is possible to ignite the vapour above the liquid. In other words, the flammable gas concentration above the liquid is close to the lower explosive limit. Determination of the flash point is done with a special apparatus and according to specific rules. ‘A sample of liquid is gradually heated in a special pot and a small flame is repeatedly and momentarily applied to the surface of the liquid. The temperature is recorded when a small flame initiates a flash or flame across the liquid surface, thereby indicating the presence of a flammable gas. In this test, the space above the liquid is Kept closed except for the brief moments when trying ignite the liquid’s surface. This test is called "Closed cup Flash Point” When we do the test with the liquid surface permanently open to the atmosphere, the result of such a test is called “Open cup Flash Point’ Because of the greater loss of gas to the atmosphere in the open cup test the open cup flash point is always a little higher (about 6°C) than the closed cup flash point. The restricted loss of gas in the closed cup apparatus also leads to a much more consistent result than can be obtained in open cup testing. For this reason, the closed cup method is generally favoured. However, open cup test figures, still may be found in the registration of various national administrations, in classification sociely rules and other such documents. Ba Scapa 45, Troportaionof Choma i Bulk 2Chapter 3 HAZARDS Transportation of Chemicals in Bulk (Tankerman Highest Grade) Department/Author: Approved by: Kjell Vagtberg Erik Frette Seagull ‘Seagull 20007 SEAGULL AS All rights reserved No part of this work covered by the copyright hereon may be reproduced or otherwise copied without prior written permission of SEAGULL AS Miscou AS Transporation of Chemicals in BulkDOCUMENT STATUS Fle:K6-Traning'St-Manualer og underfeg\Tanker Compendium Chapt 09 Hazards doc Issue No._|Date/Year_| Inc. b Issue No. | Date/Year_|_Inc. by 1427B 05. June07] KV ChemicalsiRevision 200701 Advanced Chemical CHANGES IN DOCUMENT Issue Paragraph Paragraph Heading! No. No. Deseription of Change B Updated in accordance with new regulations, miscegul Transportation of Chemicals in Bulk aTABLE OF CONTENTS Page Diagnosis of poisoning - general principles. The late stage. eestunnensn 14 12 1.3 Gassing incidents 1.4 Toxicity of inert gas. 15 16 Oxygen deficiency. Solvents and the nervous system. HAZARDS TO THE ENVIRONMENT. 3.2.1 Marine pollution 32.2 Oil 3.2.3 Heavy Metals.. 3.2.4 — Synthetic Organic Chemicals .. 3.25 Sewage 3.2.6 — Oregano-chlorines 3.3 REACTIVITY HAZARDS 3.3.1 General. 3.3.2 Self-reaction and reaction with air 3.3.3 Special precautions for inhibited cargoes: 3.3.4 Special Precautions for cargoes which require exclusion of air... 3.3.5 Reactivity with other cargoe: 3.3.6 Guidance when sufficient reactivity data is not available 3.3.7 Reaction with water. . 3.3.8 Tank Cleaning with Water 3.4 FLAMMABILITY AND EXPLOSIVITY HAXARDS 3.4.1. Fire hazards and precautions 3.4.2 Flammable properties of chemicals... 3.4.3 Too rich mixtures.. 3.4.4 Too lean mixtures. 3.45 Vapor concentrations during operations 3.4.6 During loading into a non gas-free tank 3.4.7 Ballasting a non gas-free tank 348 Gas-freeing. 3.4.9 Auto-ignition 3.4.10 Accuracy of flammable limits ©COR®NVVNNN OO aeons = For further information please see CBT # 0032 Liquid Cargo Properties, CBT # 0048 Gas Measurement, CBT # 0104 Use of Nitrogen and CBT # 0007 Inert Gas Generator secu Transportation of Chemicals in Bulk u3. HAZARDS: 3.1. HEALTH HAZARDS The officers and crew of a ship regularly carrying chemicals ought to have been trained in the general hazards involved and should be aware, therefore, of the necessary precautions to be observed. Equally, they should have been instructed about the safety rules and the first aid procedures to be used in case of an accident. In the case of other ships, it is essential that, before a chemical is handled, the officers and crew involved should be advised by the master of the hazards of the particular chemical and the action to be taken in the event of an accident. The dangers of smoking, drinking, taking food or being under the influence of alcohol or drugs whilst handling chemicals should be emphasised. If, during the handling of chemicals, any person shows signs or symptoms suggestive of poisoning, he should be taken off the work, given treatment in accordance with the advice given in this Guide and seen as soon as possible by a doctor. In the case of poisoning whilst at sea, medical advice by radio should be sought if so advised in this Guide, but in any event, the patient should be seen by a doctor at the next port of call. It should also be remembered that help might also be available from another ship if there is one within the vicinity with a physician or other trained person on board 3.1.1 DIAGNOSIS OF POISONING - GENERAL PRINCIPLES The diagnosis of poisoning may be simplified if one or more of the following factors points to the probable cause: » The circumstances of the incident, e.g. a leakage of chemicals 1 The nature of the illness, and its relationship in time to recent exposure to a chemical. ! More than one person is involved and all develop a similar illness. It must be realised, however, that: + The effects of some poisons resemble those of natural illness, e.g. vomiting and diarrhoea, or collapse. 1 Because a ship is carrying a cargo of chemicals, it does not follow that the cause of the illness is that cargo, and, unless there is evidence of a leakage, it is improbable. | Different individuals may be exposed to the poison at different times, or to a different extent during a single episode, and they may as a result become ill at different times or to differing degrees. Miseogut Transporation of Chemicals in alk 1Individuals react differently to poisons according to their health, constitution, and to how much of the poison they were exposed In a typical case of poisoning, three stages of the illness may be distinguished: 1. The latent stage - This is the interval of time from the moment of entry of a poison into the body until the first symptoms (feelings) or signs are apparent. These usually ‘occur rapidly after exposure, but in some cases, there may be a delay of several hours before they develop. In very rare instances with specific chemicals, the symptoms and signs may be delayed for some days. 2. The active stage - The signs and symptoms of the poisoning are apparent. In many cases, these are common to a great number of different chemicals, which therefore have to be treated in a general way. Chemicals can either act locally at the point of contact with the body or be absorbed from the point of contact, causing more general symptoms. This is particularly true of chemicals, which can cause local ski imitation, but are also absorbed through the skin to produce general, or specific, tox symptoms and signs. The same principle is true for other routes of entry into the body, although general symptoms are less likely to occur with eye contact. The main routes of exposure are: ' Skin contact. 1 Eye contact. 1 Inhalation - into the mouth, nose, throat and lungs | Ingestion - swallowed chemicals. The general symptoms of poisoning include: 1 Headache. 1 Nausea and vomiting | Drowsiness, ' Changes in mental behaviour. 1 Unconsciousness. "Convulsions. 1 Pain Signs of severe poisoning are: ' Arapid and weak pulse. 1 Grey or blue colour of skin Miseogut Transporation of Chemicals in alk 21 Severe difficulty in breathing, 1 A prolonged period of unconsciousness 3.1.2 THELATE STAGE The signs and symptoms usually resolve after a few hours in the majority of incidents, particularly if the degree of exposure is small. If a greater amount is absorbed or the period of exposure is prolonged, or the chemical is very toxic, symptoms may persist for some hours or even days. The patient's condition may deteriorate due to complications, the most common of which are: 1 Asphyxia. 1 Pulmonary oedema. | Bronchitis. 1 Pneumonia. 1 Circulatory collapse. ' Heart failure. 1 Liver failure. 1 Kidney failure. Death may occur despite treatment. 3.1.3 GASSING INCIDENTS If the brain does not for any reason carry out its duties, signs of failure of brain function appear, such as loss of consciousness and inability to speak and move, followed by weak breathing. Finally, if the deep centers in the brain do not work, breathing stops, the heart stops and the person dies, The control of breathing and heart beat lies in the deep central part of the brain above the "tail" which forms the spinal cord. If this area of the brain is deprived of oxygen, or in the presence of enough oxygen is poisoned by a substance which has been breathed in or swallowed, then breathing and heart-beat will fail. The sequence of events will be similar in all cases, whether brain failure is due to lack of oxygen or to poisoning, but the rate of failure may vary from the shortest time of about 4 minutes up to some hours. In so-called "gassing incidents", the usual indications of lack of proper brain function will probably be "drunken behavior’, followed by staggering, loss of consciousness, and finally stopping of breathing and heart-beat. Miseogut Transporation of Chemicals in alk 23.1.3.1 Types of "gassi 1g incidents” The mechanism of "gassing incidents" may be: 1) lack of oxygen 2) gas or vapor inhalation, together with adequate amounts of oxygen 3) gas or vapor inhaled, but with inadequate amounts of oxygen These situations are now examined in more detail 1) Lack of oxygen Air contains about 21% of oxygen, a very small amount of carbon dioxide and other gases, and the rest is nitrogen. Total lack of oxygen will result in death in about 4 to 6 minutes. If there is some ‘oxygen present but not enough to sustain life, death will probably occur fairly rapidly because the body - and particularly the brain - cannot sustain an oxygen debt for any length of time. 2) Gas or vapor inhaled together with adequate amounts of oxygen. In the presence of adequate amounts of oxygen, the harmful effects on the body of toxic gases or vapors will be solely due to the gases or vapors, and not to lack of ‘oxygen. The exact toxic effects, which are produced, will depend on the gas or vapor and how it affects the body. 3) Gas or vapor inhaled but inadequate amounts of oxygen present. in this case there are two factors operating; first the effects of the gas or vapor and second, lack of oxygen. In these circumstances what happens will depend on the toxic properties of the gas or vapor in the particular concentration present, and on the ‘extent of the lack of oxygen. The two kinds of effect will generally be additive in the production of harmful effects, with any serious oxygen lack quickly leading to Unconsciousness and death if the condition is not swiftly corrected. 3.1.3. Toxicity OF INERT GAS Cargo tanks filled with an inert atmosphere must be ventilated with air before they are . both to increase the oxygen content from less than 5% by volume to 21 % by volume and to sufficiently reduce the amounts of carbon monoxide, nitrous gases and sulphur dioxide. Carbon monoxide (CO) may typically be present in a concentration of about 0.01 % by volume in inert gas, corresponding to too ppm. In certain cases it may become significantly higher. The concentration must be reduced to below the TLV of 35 ppm by dilution or by displace with air. Carbon monoxide poisoning is caused by carbon monoxide combining with the bloods hemoglobin instead of oxygen, so that the blood loses its ability to take up oxygen in the lung This results in internal suffocation, and death ‘occurs when 60 to 70% of the hemoglobin has combined with carbon monoxide. The Miseogut Transporation of Chemicals in alk ‘symptoms are headache and drowsiness, deterioration consciousness and vomiting. In the treatment of carbon monoxide poisoning it is of the utmost importance to supply ‘oxygen, if necessary in combination with artificial respiration Nitrous gases are present as nitrogen monoxide (also known as nitric oxide) (NO) and nitrogen dioxide (NO;) in concentrations of about 0.02% by volume in inert gas after it has passed through the scrubber, corresponding to 200 ppm. The TLV for nitrogen monoxide is 25 ppm and that nitrogen dioxide is 5 ppm by volume. Nitrous gases form acids by reaction with the moisture the air, and may destroy the lung tissue. The sulphur dioxide content of inert gas will be very low, provided the scrubber is efficient. 3.1.4 OXYGEN DEFICIENCY Oxygen deficiency must always be suspected in any enclosed space which has not been ventilate for some time. It may be caused by vapor emitted from volatile liquids, by the displacement air by inert gas or by the consumption of the available oxygen in the air by chemical reactions Su as rusting or the drying of paint. Air contains 21 % ‘oxygen, and spaces should not be entered before establishing that the oxygen content of the atmosphere that is to be entered is in fact 21 % 3.1.5 SOLVENTS AND THE NERVOUS SYSTEM The nervous system in the human body consists of the brain, the spinal cord and the peripheral nerves. The main part of the brain (cerebrum) controls thought, the movements and the sensations of the body. A smaller part of the brain (cerebellum) controls the balance of the body and finer movements. The spinal cord is connected to the brain. Peripheral nerves branch out from it and enter muscles and cells throughout the body. These nerves transmit signals to and from the brain, 3.1.6.1 The nervous system — what is it? “Organic solvents" is an expression used as a common name for a large number of chemicals. These chemicals dissolve fat and evaporate easily. They are composed of carbon and hydrogen. Organic solvents are useful chemicals. They exist in paint, lacquer, glue and many chemicals used for cleaning. They are important in the production of plastic and several similar compounds. Some examples of organic solvents are: Acetone, benzene, ethanol styrene, toluene, trichloroethylene, white spirit and xylene. 3.1.6.2 Occupational solvent intoxication The organic solvents evaporate easily, and this makes them easy to inhale. The solvents may pollute working environment, and may enter the lungs of the workers. From the lungs the solvents enter the blood. In addition, organic solvents may enter the blood by penetrating the skin. The blood transports the solvents to different parts of the body, including the nervous system Miseogut Transporation of Chemicals in alk ‘3.1.6.3 Acute Intoxication When the concentration of organic solvents is too high in an environment, this may give rise to symptoms of acute poisoning in exposed workers. Common symptoms of a beginning acute intoxication are: Tiredness or feeling "high", headache, nausea and dizziness. If the concentration of the solvents reaches certain levels, the exposed workers may lose consciousness and die. 3.1.6.4 Chronic Intoxication Exposure which consists of the inhalation of organic solvents over a long period may give rise to the “chronic organic solvent intoxication syndrome". Workers with this condition develop symptoms which exist whether or not they are exposed to solvents at the time. Typical symptoms of chronic organic solvent intoxication affecting the main part of the brain are: An abnormal fatigue, reduction of memory, concentration difficulties, irritability, depression, anxiety, headache and dizziness. If the cerebellum is affected, this may lead to an unsteady gait. When the peripheral nerves are affected, there may be reduced muscular power and loss of sensation in arms and legs. in addition, reduced sexual desire and impotence may be caused by a chronic solvent intoxication. 3.1.6.5 The chronic organic solvent intoxication syndrome No cure for this syndrome exists. Still, the diagnostic work is of great importance. A person with this syndrome must avoid further exposure to organic solvents to present the development of further damage in the nervous system There are several difficulties connected to the diagnostic procedure of this syndrome. There is no specific test which confirms the diagnosis. Several other diseases may give the same kinds of symptoms as this syndrome. Several tests and examinations are needed to evaluate these patients properly. Specialists in occupational medicine and neurology are needed for the diagnostic work. To develop this syndrome, a person must have been exposed to organic solvents regularly for many years. The syndrome gives typical symptoms like those described under the heading “chronic intoxication". To diagnose this syndrome, signs of disease in the nervous system must be found by the examination of the brain and/or the peripheral nerves. Examinations used to diagnose the syndrome are a neurological ‘examination, tests of the electrical activity of the brain, computerized tomography of the brain, examinations of the spinal fluid, psychological tests and tests of nerve conduction velocity of nerves in arms and legs. To diagnose the syndrome, no other disease must be found which may explain the existing symptoms and signs of disease in the patient, Miseogut Transporation of Chemicals in alk ‘3.2 HAZARDS TO THE ENVIRONMENT The fact that some cargoes in chemical tankers may cause a severe environmental hazard if released to the sea, to land or to the air. International regulations for the control of marine pollution by cargoes from chemical tankers are set out in Annex II of MARPOL 73/78 and in the IBC code. 3.2.1 MARINE POLLUTION Marine pollution is the introduction by humans of substances or energy into the ‘oceans that change the quality of the water or affect the physical and biological environment. There are many different substances, which pollute the oceans. We will examine the effects of oil, heavy metals, synthetic organic chemicals, sewage and oregano-chlorines. 3.2.2 On Many different factors determine the effect of an oil spill. The consequences of a spill are determined by its location, the quantity and concentration of the oil, the season of the year, currents and other factors. The crude oil spills are usually more frequent and larger in volume. The little components of crude oil that do not dissolve in water, harms juvenile forms of marine organisms, even in small concentrations. The remaining undissolved components, the majority of crude oil, forms sticky layers on the surface which prevents the free diffusion of gases, clogs adult organisms’ feeding structures, and decreases the sunlight available for photosynthesis. Most forms of marine life recover within about five years, as crude oil is not highly toxic and it is biodegradable. Refined oil near the shore can be more disruptive for longer periods of time. These spills lead to high number of marine organisms’ death and environmental damage that leads to reduced species diversity and fertility. Some areas, after three decades, are not recovered from spills of refined oil Although intertidal and shallow water subtidal communities are most sensitive to oil spills, bottom organisms are also affected. Volatile components of an oil spill eventually evaporate into the air, leaving heavier tars behind which forms into tar balls. These balls fall to the bottom and may be assimilated by bottom organisms or incorporated into sediments. There are many methods to contain and clean up an oil spill, however, sometimes they are dangerous and damageful. Detergents used to disperse oil are especially harmful to living things. 3.2.3 Heavy MeTaLs Heavy metals are a great concern because they enter the food chain. Some dangerous metals being introduced into the ocean are mercury, lead and copper. Mercury and lead poisoning cause brain damage and behavioural disturbances in children. Copper is also dangerous to marine organisms; it has been used in marine anti-fouling paints. 3.2.4 SYNTHETIC ORGANIC CHEMICALS Many different synthetic organic chemicals enter the ocean and become incorporated into organisms. Ingestion of small amounts can cause illness or death Miseogut Transporation of Chemicals in alk 7Halogenated hydrocarbons are a class of synthetic hydrocarbon compounds that contain chlorine; bromine or iodine is used in pesticides, flame-retardants, industrial solvents and cleaning fluids. The level of synthetic organic chemicals in seawater is usually very low, but some organisms can concentrate these toxic substances in their flesh at higher levels in the food chain. That is an example of biological amplification. DDT causes this ‘occurrence. Polychlorinated biphenyl's (PCB') also create biological amplification. It was used to cool and insulate electrical devices and to strengthen wood or cement. 3.2.5 SEWAGE Sewage sludge, a mixture of organic matter containing viruses and bacteria, synthetic organic chemicals and toxic metal compounds, is dumped into the ocean. Sludge can combine with oxygen to produce an oxygen poor environment where few animals can survive. During storms some of this material washes up on local beaches, contaminates shellfish beds and causes disease outbreaks among people. 3.2.6 OREGANO-CHLORINES 3.2.6.1 What are organochlorines? Organochlorines are substances containing chemically combined chlorine and carbon. Most are toxic, persistent and tend to bioaccumulate in the environment. These qualities make them, arguably, the most dangerous group of chemicals to which natural systems can be exposed Around 11,000 organochiorines have been identified. Very few of these occur naturally; most are produced and released by industry. Synthetic organochlorines result from all industrial processes that produce or use elemental chlorine. They are created either deliberately as a product or by-product, or incidentally after the release of other chlorinated compounds, which then react in the environment to form new and often more toxic organochiorines. 3.2.6.2 Where are they found? Chlorine production, the source of industrial organochlorine, began in 1893 and now exceeds 40 million tonnes per year. Inevitably, then, the release of organochlorines into the environment is also growing. Since the rate at which organochlorines break down to harmless chemicals is far outstripped by their rate of production, the load of organochlorines on the environment is growing each year. This represents a burden of toxic persistent chemicals of a type and on a scale that natural systems have never encountered before. Organochlorines are now present in water, in air and in living things everywhere on earth - from the deep sea bed to the stratosphere, from the Arctic to the Antarctic. The north-east Atlantic is considered to be the largest reservoir of one group of ‘organochlorines - the polychlorinated biphenyls (PCBs) - in the world. Organochlorines tend to concentrate in living tissues and especially in species at the top of the food chain. Particularly high concentrations of organochlorines have been found in the tissue of polar bears in the Norwegian Arctic. Miseogut Transporation of Chemicals in alk 1High levels have also been found in Canadian and Alaskan polar bears, in Antarctic penguin chicks, in dolphins and other cetaceans in many coastal waters, including those of the eastern US and the Mediterranean, and in seals from Califomia to southern Finland. 3.2.6.3 Their properties Most organochlorines are extremely stable. As a result, they persist in the environment for a very long time - some for hundreds of years or more. Others do not break down to any appreciable extent at all. When organochlorines do degrade they usually produce other organochlorines - and these may be more hazardous or more persistent than the original substance. Since most organochlorines are not soluble in water they tend to migrate: the more volatile ones (like CFCs) to the water surface and from there to the atmosphere; the less volatile ones (like PCBs) into sediments and from there into the food chain. Organochlorines bioaccumulate because they dissolve in fat and so build up in the fatty tissues of living things. This accumulation is then biomagnified as organisms are eaten by predators, and the burden of pollution is concentrated as it passes up through the food chain. Organochlorines that have accumulated in the fatty tissues of mammals can be transferred via the placenta or breast milk to the next generation, sometimes in large concentrations. It has been estimated that residues passed on in this way, even with no direct exposure after the first generation, would still be detectable after five generations. Organochlorines are highly toxic, Because they are largely foreign to nature, most living things have not developed any specific methods to break them down and get rid of them. They act in several ways to interfere with some of the most fundamental biological processes. They ‘can cause reproductive failure and infertility in females; impair the development of offspring; lead to feminization and demasculinization of males; disrupt the immune system, leaving organisms more susceptible to disease and infection; contribute to the development of cane and damage the nervous system, liver, kidneys and other organs. 33 REACTIVITY HAZARDS 3.3.1 GENERAL Special consideration has to be given to the possibility of chemicals undergoing a chemical or physical reaction during cargo handling and transport conditions thereby creating additional hazard, Chemical reaction may produce heat which in turn may accelerate the reaction, may cause the release of a large volume of vapor and/or pressure rise, or may cause the formation of flammable and/or harmful vapors that otherwise would not be expected. In principle, the dangers arising from chemical reaction are those of increased fire and health hazard Three main types of reaction have to be considered: (a) Self-reaction and reaction with air where only the particular chemical itself is involved. Small amounts of other chemicals or contact with certain metals may promote reaction. Polymerization is a common type of self-reaction. Miseogut Transporation of Chemicals in alk ’(b) Reaction as a result of mixing one chemical with another. Neutralization of an acid with an alkali is a typical example of one chemical reacting with another. A cargo which is self-reactive as in (a) may also react with other cargoes. (©) Reaction as a result of mixing with water. A cargo which is self-reactive as in (a) or reacts with others in (b) may also react with water. 3.3.2 SELF-REACTION AND REACTION WITH AIR Self-reaction or reaction with air can occur in the liquid, in the vapor or in both. Reaction may be promoted by heat and by the presence of certain metals and other cargoes in small amounts. Control of temperature and the avoidance of unsuitable materials in the cargo system and contamination by even small amounts of other cargoes all contribute to the safe carriage of self-reactive cargoes. Reaction in the liquid can be retarded by inerting or by adding to it a small amount of a specific chemical known as an inhibitor. Those cargoes which in pure form can undergo a vigorous self-reaction (usually resulting in polymerization) may only be offered for transportation provided they contain an inhibitor. An inhibitor added to the liquid generally will not retard reaction in the vapor or condensed vapor in the ullage space. Displacing air (oxygen) from the ullage space with inert gas will retard reaction of the vapor therein and inerting may be an additional requirement, even if the cargo contains an inhibitor. For certain other cargoes, an essential safety requirement to avoid reaction is to prevent liquid and vapor from coming into contact with air at all times during cargo handling and transport. 3.3.2.1 General Precautions for self-reactive cargoes and cargoes which react dangerously with air (a) The cargo tanks and cargo handling system should be free of the metal components which are listed in the data sheet as unsuitable, (b) If the maximum cargo temperature during loading and on voyage needs to be controlled the master should verify what the limit is and what means are available to ensure that it will not be exceeded during cargo handling and on the voyage. Cargo temperature should be measured regularly and cooling systems put into operation when necessary. Loading should be stopped if the temperature of the cargo being received exceeds the limit (©) __ Even if temperature control is not a specific requirement it is recommended that self-reactive chemicals are never stowed in tanks directly adjacent to heated cargoes nor handled through pipe-lines which pass through tanks containing heated cargoes. Also it is recommended that cargo tanks top are kept cool by water spray when ambient temperatures are high, thereby to retard reaction in the vapor space. Miseogut Transporation of Chemicals in alk 0(4) Before loading, the cargo tanks and cargo handling system should be thoroughly cleaned to remove other cargoes that may promote self-reaction of the cargo to be loaded. 3.3.3 SPECIAL PRECAUTIONS FOR INHIBITED CARGOES When the cargo requires to be inhibited as a condition of safe transport, the following addition precautions should be taken: (2) _ The Master should verify with the shore representative that the cargo will be correctly inhibited before loading, otherwise loading should be refused. (b) The Master should also verify that the concentration of inhibitor will be sufficient to prevent dangerous reaction during the voyage taking into account its duration and expected or required maximum cargo temperature (c) If inhibitor is likely to be consumed or if regular checking of the cargo for inhibitor concentration during the voyage is advised, the master should ensure that sufficient stock of inhibitor is put on board before sailing, for addition to the cargo as necessary, together with instructions for introducing it. If regular analysis is advised proper instructions should be obtained from the shore representative on the method of analysis. (4) Care should be taken during the handling of the inhibitor which may present health hazard. (€) Special attention should be given during the voyage to the cargo tank vent system which may become blocked by solid reaction products. 3.3.4 SPECIAL PRECAUTIONS FOR CARGOES WHICH REQUIRE EXCLUSION OF AIR When inerting to exclude air from the cargo system it is essential for safe carriage, that the following additional precautions should be taken: (2) The cargo handling system for the intended tank(s) should be independent of all others and cross-connection by accident should not be possible. (b) The cargo should be handled in a closed system, with a closed ullage or other arrangement to minimize the escape of vapor or ingress of air. Vapor or gas displaced during loading preferably should be retuned ashore by vent line. (©) __ Before loading, the oxygen concentration in the cargo tank(s) and associated handling system should be reduced below the permitted maximum by purging with inert gas. (4) The inert gas supplied by ship or shore should be of high purity. Preferably nitrogen should be used although other gases or vapors may be considered. Inerting of the cargo spaces only at the loading port may not be sufficient and a quantity of additional inert gas should be carried on board in order to maintain a proper inert atmosphere in the event of normal loss or leakage from the cargo space. Miseogut Transporation of Chemicals in alk 0(e) The Master should ascertain the maximum oxygen concentration permitted in the cargo space at any time during cargo handling and on voyage and that means are available for measuring it. When it is a requirement, the oxygen content in the space should be reduced below the limit before loading stars. (f) The cargo may be discharged by pumps but inert gas and/or cargo vapor should be supplied to the tank during cargo discharge. Alternatively, the cargo may be discharged by inert gas pressure but only provided the working pressure of the cargo tank and handling system is not exceeded. Alir pressure should never be used for cargo discharge or to assist in cargo discharge. (@) On completion of cargo discharge, the ship/shore hose connection should be cleared of cargo with inert gas before disconnecting. The tanks should be closed and kept inert unless they are to be gas-freed for any purpose. (hb) Awater supply should be ready for immediate use during cargo handling to wash away spillages. @ If gas-freeing is necessary after cargo discharge the operation should be conducted preferably alongside with the displaced vapor being retumed ashore for venting. If this is not possible vapor should be released through vents terminating well above deck level. 0 If a tank first has to be washed for cleaning, the washing operation should be carried out when the tank is still inert. Then the tank should be gas-freed by purging with inert gas until cargo vapor has been largely removed, followed by air until the tank is free of vapor and the oxygen content restored to normal atmospheric level (21%) 3.3.5 REACTIVITY WITH OTHER CARGOES To establish whether or not two cargoes will react dangerously together, the data sheets for both cargoes should be consulted. When the data sheet indicates that a dangerous reaction may result by mixing the cargo in question with another, "double" separation should be provided as greater security against accidental mixing. "Double" separation involves: 1) pump room, cofferdam or similar void space (which may be an empty cargo compartment) between tanks or compartments containing incompatible cargoes, OR at least one compartment loaded with a cargo compatible with each, and separating, the incompatible cargoes, AND 2) independent cargo pipelines to each compartment containing incompatible chemicals and which do not pass through any compartment containing other incompatible cargoes unless the pipeline is in a tunnel or similar arrangement, AND Miseogut Transporation of Chemicals in alk B3) independent vent systems on each compartment containing incompatible cargoes. 3.3.6 GUIDANCE WHEN SUFFICIENT REACTIVITY DATA IS NOT AVAILABLE Those responsible for soliciting, booking and scheduling parcel cargoes of chemicals should always satisfy themselves that the various parcels scheduled for any given voyage of any given ship are mutually compatible and can safely be loaded and carried within the normal segregation of the ship. Since the ultimate responsibility for safety of the vessel lies with the Master, he should assure himself by inspection of the data sheets that the cargo distribution proposed for any voyage provides proper segregation of all parcels from the standpoint of compatibility. If the data sheets do not provide the necessary information, the Master should defer loading of the cargo until he has been able to consult with his owner, and received satisfactory assurance that the cargoes to be loaded and the proposed plan of segregation are indeed compatible and safe. It cannot be emphasized too strongly that parcels of chemicals should not be accepted for shipment or loaded on a vessel unless positive assurance is available that the various chemicals are compatible within the basic patter of segregation of the vessel itself 3.3.7 REACTION WITH WATER The data sheet indicates if a dangerous reaction is possible between a chemical and water. If such a reaction is possible "double" separation between the chemical and water is recommended. “Double” separation involves: 1) double skin as provided by a double bottom and side cofferdam between the cargo and the sea, AND 2) a cofferdam or similar void space (which may be an empty cargo compartment) to separate the tank containing the cargo from tanks containing water, OR at least one compartment loaded with a cargo which question and with water, compatible with the cargo in AND 3) pipelines serving the cargo tank should be independent from lines serving any tank containing water and should not pass through any tank containing water, or vice versa unless the pipeline is in a tunnel or similar arrangement, AND 4) _ vents systems serving the tanks containing the cargo should be independent from vent systems serving tanks containing water, Miseogut Transporation of Chemicals in alk B3.3.8 TANK CLEANING WITH WaTER If a cargo tank has contained a chemical that reacts dangerously with water, tank cleaning with water should only be undertaken in the manner specified by the shipper or by some other safe means. If toxic vapors are evolved on contact with water, then breathing apparatus may be required by those involved in the operation 3.4 FLAMMABILITY AND EXPLOSIVITY HAXARDS. Most cargoes in chemical tankers are flammable, and their vapors may therefore form flammable mixtures. 3.4.1 FIRE HAZARDS AND PRECAUTIONS Measures for the prevention of fire and explosion involving cargo are dependent on preventing cargo vapor and sources of ignition coming into contact. Cargo vapors in flammable concentrations are to be expected in the recognized hazardous areas such as cargo tanks, pump rooms, and, at times on the tank deck around openings from cargo tanks. Strict elimination, by design, of all possible sources of ignition from these areas is essential. On the other hand, living accommodation, galley and engine room, are spaces where sources of ignition are inevitably present because of electrical equipment, boiler fires etc., and it is essential to avoid the entry of flammable cargo vapor into such spaces. Personnel should be continuously on their guard not only against the more obvious dangers but also against unforeseen circumstances which could lead to flammable vapors and sources of ignition coming into contact, 3.4.2. FLAMMABLE PROPERTIES OF CHEMICALS The vapor given off by a liquid bums, and not the liquid itself. A mixture of vapor and air cannot be ignited unless the proportion of vapor and air lies between two concentrations known as the Lower Flammable (Explosive) Limit (LFL or LEL) and the Upper Flammable (Explosive) Limit (UFL or UEL). The limits depend upon the cargoes (see data sheets). Concentrations below the lower limit (too-lean), or above the upper limit (too-rich), are incapable of burning, but it is important to remember that concentrations above the upper limit can be made to burn by diluting them with air until the mixture is in the flammable range. Vapor concentrations depend upon the vapor pressure and temperature of the liquid. As the temperature increases so does the vapor pressure and vapor concentration above the liquid. For each liquid there is a temperature at which the vapor concentration reaches the LFL, and another, higher, temperature at which the concentration exceeds UFL. The more readily the liquid vaporizes, the lower the temperature at which the LFL is reached 3.4.3 Too RICH MIXTURES A too rich mixture is safe for as long as the tank remains closed and intact. Even if a fire occurs in an adjacent tank the too-rich mixture cannot catch fire provided that it, remains too-rich. Miseogut Transporation of Chemicals in alk‘A too-tich mixture is no guarantee of safety under all conditions. For example, in the ‘event of a tank being ruptured in a collision or following an adjacent explosion, air is likely to enter the tank and may dilute the gas to a flammable concentration. The resulting flammable mixture may then be ignited by hot metal or sparks associated with the rupture. 3.4.4 Too LEAN MIXTURES Too lean mixtures will not support combustion but are no guarantee of continued safety. For example, if the temperature increases sufficiently any oil which is present may be raised above its flash point thus producing a flammable mixture. Such temperature variations may occur when a non-volatile oil needs to be heated prior to discharge. A sufficient increase in temperature may also cause residual oil in an ‘empty dirty tank to evolve flammable concentrations of vapor. This might happen if an adjacent cargo is being heated or if an adjacent tank is being steamed or hot washed. Repairs in a tank or pump room can easily change a too-lean condition to one which is flammable. For example, when a pipe or pump containing volatile oil is opened up, oil may run into the compartment, thus producing a flammable concentration of vapor. EEE SIS PO ed GPU cma Ro io) « Flammable gas molecules « Oxygen molecules Miseogut Transporation of Chemicals in Bale 1sThe flash point of a liquid is an indication of the temperature at which a liquid produces sufficient vapor to give a concentration in air equivalent to the LFL. Some cargoes form flammable mixtures at all ambient temperatures; others only at higher ambient temperatures and others again only when heated. For the purposes of the safe handling procedures dealt with in this guide, the flammability characteristics of cargoes are divided into three broad categories according to the flash point: Flammable cargoes-those with a flash point below 60° C, = Combustible cargoes-those with a flash point above 60° C. = Non-Combustible cargoes-those which have no flash point and do not burn. The above description of flammability considers cargo vapor being mixed with air. If air is mixed with sufficient inert gas such as nitrogen or carbon dioxide, its oxygen content will no longer be capable of supporting the combustion of chemical vapor. Suppression of combustion by this means is known as inerting and is a measure which may be recommended or otherwise adopted for preventing ignition of vapors within enclosed spaces such as cargo tanks. It is important to remember that an inerted mixture may become flammable on mixing again with air, for instance on venting the mixture to atmosphere or during gas-freeing with air. Miseogut Transporation of Chemicals in alk 16ee a) ‘| Peso) Bt Ty Perea) freer T ta) $ | : FLAMMABILITY — LIMITS AND RANGE 3.4.5 VAPOUR CONCENTRATIONS DURING OPERATIONS This section describes when dangerous concentrations of vapor-either flammable or over-tich are likely to be encountered during normal operations. 3.4.5.1, During Loading into a Gas-Free Tank A cargo being loaded at a temperature below its flash point will not produce a flammable vapor concentration either within or outside of the tank but with some cargoes excessive turbulence or splashing at the commencement of loading may form a flammable mist above the liquid surface. ‘Above the flash point, and depending upon the liquid temperature and vapor pressure at that temperature, a flammable or over-rich mixture will be produced within the tank, unless it has been inerted, and which will tend to remain as a layer over the liqui ‘except when the chemical vapor density is less than that of air. The higher the vapor Miseogut Transporation of Chemicals in Buk npressure the greater the depth and concentration of vapor in the layer. Although the layer itself r may be over-rich there will be a flammable mixture where it meets the air above. Mixing of the vapor with the air above is slow and the heavy vapor rises as a layer as. the liquid rises. The gas being displaced from the top of the tank and entering the venting system will be initially air and little cargo vapor will be expelled in the early stages of loading. Eventually the concentration of vapor increases and finally flammable or over-rich mixture will be expelled. By dilution with air outside of the tank over-rich mixture will become flammable. Venting of flammable or over-rich mixtures from tanks during the later stages of loading creates potentially a most dangerous situation. Vaporization adds to the total volume of gas expelled through the vent system as the cargo is loaded. With a properly designed vent system the increased rate should not create an unacceptable excess pressure in the tank. The foregoing applies only to cargoes which are being handled at temperatures below the boiling point. If a cargo is loaded into a tank at atmospheric pressure and at a temperature above its boiling point, boiling will start immediately with rapid and sustained evolution of vapor. Shortly after loading starts, vapor in high concentrations will be vented from the tank and the amount of vapor may be such that unacceptable pressure is caused in the tank. When the cargo temperature exceeds the boiling point cargoes should only be loaded into special tanks. 3.4.6 DURING LOADING INTO A NON GAS-FREE TANK The vapor concentration inside a tank which has not been gas-freed depends upon the previous cargo, the amount of liquid cargo left in the tank, the time elapsed since discharge was completed, and on temperature. If the previous cargo was loaded at, or reached during the voyage, a temperature above its flash point, a flammable or over-rich mixture should be suspected throughout the tank. The mixture will be displaced through the vent system by the incoming cargo, whatever the cargo. 3.4.7 BALLASTING ANON GAS-FREE TANK Vapor concentrations will be expelled through the vent system as in 3.4.6. Even if the cargo is water-soluble the same situation will apply since the vapor is unlikely to be absorbed quickly. 3.4.8 GAS-FREEING Vapor concentration in the tank before gas-freeing starts is dependent on the factors in 3.4.6. Removal of flammable or over-rich vapor presents a potentially hazardous situation since irrespective of the method of gas-freeing such vapor mixtures will be expelled from the tank. Mechanical ventilation, rather than natural ventilation, is recommended to minimize the period of danger and ensure the rapid dispersion of vapor. Miseogut Transporation of Chemicals in alk in3.4.9 AUTO4GNITION The vapors from flammable and combustible liquids (including oil fuel and lubricating oil) may ignite if the liquids come into contact with a surface heated above the auto- ignition temperature e.g. steam lines, overheated equipment, despite the absence of external flame or spark. In any case the fire hazard will be increased by the greater evaporation. Immediate steps should be taken to remedy any leakage which may result in the liquid coming in contact with the hot surfaces. Care should also be taken to avoid rags or other materials soaked in oil or chemical coming in contact with hot surfaces 3.4.10 ACCURACY OF FLAMMABLE LIMITS Flammable limits may be expressed in terms of percentage volume or percentage weight. The resulting limits are slightly different. In this book, flammable limits are quoted as a percentage of the total volume of the mixture. Flammable limits, for any given cargo, or in other publications should not be used as safety limits because the laboratory conditions under which they were established may not be the same as conditions existing in cargo tanks. Flammable limits vary with: volume of the container in which combustion takes place temperature of the mixture pressure of the mixture oxygen concentration in the air which makes up the mixture direction of propagation of a flame Miseogut Transporation of Chemicals in alk »eee cir eer Uppar flammable init 14% sete Ht} Flammability diagram for methane Miseogut Transporation of Chemicals in Buk 20Chapter 4 RULES AND REGULATIONS Transportation of Chemicals in Bulk (Tankerman Highest Grade) Department/Author: Approved by: Kjell Vagtberg Erik Frette Seagull Seagull 20007 SEAGULL AS All rights reserved No part of this work covered by the copyright hereon may be reproduced or otherwise copied without prior written permission of SEAGULL AS Gad Bsc 45 raaportaon of Chemical x BulkDOCUMENT STATUS. 0g. undrlagiTanker Operation ~ Chen \Revislen 200701 Advanced Chemical Compendium Chapt 04 Rules ond Requations doo Issue No. | Date/Year | _ Inc. by Issue No. | Date/Year | _ Inc. b 14278 | 05. June kv 07 CHANGES IN DOCUMENT Issue Paragraph Paragraph Heading! No. No. Description of Change Updated in accordance with new regulations. Transportation of Chem ule ATABLE OF CONTENTS Section Page 4, RULES AND REGULATIONS 4 4.2 _ INTERNATIONAL AND NATIONAL CODES AND REGULATIONS .. 1 4.1.1 IMO: what itis, what it does and how it works. 1 4.1.2 What it does. a ond 4.21 — Safety - SOLAS. 2 4.1.3 Preventing pollution - MARPOL 73/78 3 4.1.4 IMO's codes & recommendations 4 4.1.5 Dumping at sea 4 4.1.6 How it works. 5 41.7 The future 5 4.2 BULK CHEMICAL CODES 6 4.21 The BCH Code. 6 4.2.2 The IBC Code oe 6 4.2.3 New ship — Existing ship 6 4.24 — Extract from the IBC Code 7 4.3 ANNEX I OF MARPOL 73/78 1 4.3.1 Regulation 1 - Definitions. "1 43.2 Regulation 2- Application 14 4.3.3 Regulation 4 - Exemptions. 14 4.3.4 Regulation 6 - Categorization and listing of noxious liquid substances and other substances. . ese 16 4.3.5 Regulation 11 - Design, construction, equipment and operations........17 4.3.6 Regulation 12 - Pumping, piping, unloading arrangements and slop tanks 19 4.3.7 Regulation 13 - Control of discharges of residues of noxious liquid substances. 21 4.3.8 Regulation 14 - Procedures and Arrangements Manual 25 4.3.9 Regulation 15 - Cargo Record Book... - 26 4.3.10 Regulation 16 - Measures of control. 27 For further information please see CBT # 0092 MARPOL and CBT 0053 IMDG Code asus Traraportaton of Chemo Bult uw4. RULES AND REGULATIONS This chapter introduces the international and national rules and regulations affecting chemical shipping. 4.1 INTERNATIONAL AND NATIONAL CODES AND REGULATIONS The most important of the rules governing the transport of liquid chemicals in bulk are: International conventions, national regulations and classification society rules Shipping is perhaps the most international of all the world’s great industries - and one of the most dangerous. It has always been recognised that the best way of improving safety at sea is by developing international regulations that are followed by all shipping nations and from the mid-19th century; onwards a number of such treaties were adopted. Several countries proposed that a permanent international body should be established to promote maritime safety more effectively, but it was not until the establishment of the United Nations itself that these hopes were realised. In 1948, an international conference in Geneva adopted a convention formally establishing IMO. It entered into force in 1958 and the new Organisation met for the first time the following year. 4.1.1 IMO: WHATIT IS, WHAT IT DOES AND HOW IT WORKS When the establishment of a specialised agency of the United Nations dealing with maritime affairs was first proposed, the main concern was to evolve international machinery to improve safety at sea Because of the international nature of the shipping industry, it had long been recognised that action to improve safety in maritime operations would be more effective if carried out at an international level rather than by individual countries acting unilaterally and without co-ordination with others. Although a number of important international agreements had already been adopted, many States believed that there was a need for a permanent body, which would be able to co-ordinate and promote further measures on a more regular basis. It was against this background that a conference held by the United Nations in 1948 adopted a convention establishing the International Maritime Organisation (IMO) as the first ever-interational body devoted exclusively to maritime matters. In the 10-year period between the adoption of the Convention and its entry into force in 1958, other problems related to safety but requiring slightly different emphasis had attracted intemational attention. One of the most important of these was the threat of marine pollution from ships, particularly pollution by oil carried in tankers. An international convention on this subject was actually adopted in 1954, four years before IMO came into existence, and responsibility for administering and promoting it was assumed by IMO in January 1959. From the very beginning, the improvement of maritime safety and the prevention of marine pollution have been IMO's most important objectives. ical 4s Troportaionof Choma i Bulk 1IMO is a technical organisation and most of its work is carried out in a number of committees and sub-committees. The Maritime Safety Committee (MSC) is the most senior of these. It has a number of sub-committees whose titles indicate the subjects they deal with: - _ Safety of Navigation (NAV); - Radio communications and Search and Rescue (COMSAR); - Training and Watchkeeping (STW); - Carriage of Dangerous Goods, Solid Cargoes and Containers (DSC); - Ship Design and Equipment (DE); - Fire Protection (FP); - Stability and Load Lines and Fishing Vessel Safety (SLF); - Flag State Implementation (FSI); - Bulk Liquids and Gases (BLG). The Marine Environment Protection Committee (MEPC) was established by the Assembly in November 1973. It is responsible for co-ordinating the Organisation's activities in the prevention and control of pollution of the marine environment from ships. The FSI and BLG Sub-Committees are also sub-committees of the MEPC. The Legal Committee was originally established to deal with the legal problems arising from the Torrey Canyon accident of 1967, but it was subsequently made a Permanent committee. It is responsible for considering any legal matters within the scope of the Organisation. 44.2 WHAT IT DOES In order to achieve its objectives, IMO has, in the last 40 years, promoted the adoption of some 40 conventions and protocols and adopted well over 800 codes and recommendations concerning maritime safety, the prevention of pollution and related matters. The initial work on a convention is normally done by a committee or sub-committee; a draft instrument is then produced which is submitted to a conference to which delegations from all States within the United Nations system - including States which may not be IMO Members - are invited. The conference adopts a final text, which is submitted to Governments for ratification. An instrument so adopted comes into force after fulfilling certain requirements, which always include ratification by a specified number of countries. Generally speaking, the more important the convention is the more stringent are the requirements for entry into force. Implementation of the requirements of a convention is mandatory on countries which are parties to it. Codes and recommendations which are adopted by the IMO Assembly are not binding on Governments; however, their contents can be just as important, and in most cases they are implemented by Governments through incorporation into domestic legislation. 4.24 Sarety-SOLAS The first conference organised by IMO in 1960 was, appropriately enough, concemed with maritime safety. That conference adopted the International Convention on Safety of Life at Sea (SOLAS), which came into force in 1965, replacing a version adopted in 1948. The 1960 SOLAS Convention covered a wide range of measures designed to improve the safety of shipping. They included ical 4s Troportaionof Choma i Bulk 2subdivision and stability; machinery and electrical installations; fire protection, detection and extinction; life-saving appliances; radiotelegraphy and radiotelephony; safety of navigation; carriage of grain; carriage of dangerous goods; and nuclear ships. The safety of ships and their crews is IMO's greatest concern. The 1960 SOLAS Convention was the basic international instrument dealing with matters of maritime safety and, in response to new developments, it was amended several times. However, because of the rather difficult requirements for bringing amendments into force, none of these amendments actually became binding internationally. To remedy this situation and maybe introduce the needed improvements more speedily, in 1974 IMO convened a conference to adopt a new international convention for the safety of life at sea which would incorporate the amendments adopted to the 1960 Convention as well as introduce other changes, including an improved amendment procedure. Under the new procedure, amendments adopted by the MSC would enter into force on a predetermined date unless they were objected to by a specific number of States. The 1974 SOLAS Convention entered into force on 25 May 1980. 4.1.3. PREVENTING POLLUTION - MARPOL 73/78 The most important convention regulating and preventing marine pollution by ships is the IMO International Convention for the Prevention of Pollution from ships, 1973, as modified by the Protocol of 1978 relating thereto (MARPOL 73/78). It covers accidental and operational oil pollution as well as pollution by chemicals, goods in packaged form, sewage, garbage and air pollution. IMO's Intervention Convention affirms the right of a coastal State to take measures on the high seas to prevent, mitigate or eliminate danger to its coastline from a maritime casualty. The Intemational Convention on Oil Pollution Preparedness, Response and Co-operation (OPRC), 1990 provides a global framework for international co-operation in combating major incidents or threats of marine pollution. A protocol to this convention (HNS Protocol) covers marine pollution by hazardous and noxious substances, Regulations governing the carriage of chemicals by ship are contained in the International Convention for the Safety of Life at Sea (SOLAS) and the International Convention for the Prevention of Marine Pollution from Ships, as modified by the Protocol of 1978 relating thereto (MARPOL 73/78). ‘The regulations cover chemicals carried in bulk, on chemical tankers, and chemicals carried in packaged form, Carriage of chemicals in bulk is covered by regulations in SOLAS Chapter VII - Carriage of dangerous goods and MARPOL Annex Il - Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk. The present MARPOL consolidated edition, 2006 edition presents the texts and unified interpretations of the Convention, articles, protocols, and Annexes | to VI: Annex! _ - Regulation for the Prevention of Pollution by Oil ical 4s Troportaionof Choma i Bulk 3(Annex | entered into force on 2 October 1983) Annex Il - Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk ("Parties shall be bound by the provisions of Annex II of MARPOL 73/78 as amended from 6 April 1987") ‘Annex Ill - Regulation for the Prevention of Pollution by Harmful Substances in Packaged Form (Annex Ill entered into force on 1 July 1992.) Annex IV - Regulation for the Prevention of Pollution by Sewage from Ships (Annex IV entered into force on 27 September 2003.) ‘Annex V Regulation for the Prevention of Pollution by Garbage from Ships (Annex V entered into force on 31 December 1988) Annex VI - Regulations for the Prevention of Air Pollution from Ships (Annex VI entered into force on 19 May 2005.) 4.1.4 IMO's copes & RECOMMENDATIONS. In addition to conventions and other formal treaty instruments, IMO has adopted several hundred recommendations dealing with a wide range of subjects. Some of these constitute codes, guidelines or recommended practices on important matters not considered suitable for regulation by formal treaty instruments. Although recommendations -whether in the form of codes or otherwise - are not usually binding on Governments, they provide guidance in framing national regulations and requirements. Many Governments do in fact apply the provisions of the recommendations by incorporating them, in whole or in part, into national legislation or regulations. In some cases, important codes have been made mandatory by including appropriate references in a convention. These recommendations are generally intended to supplement or assist the implementation of the relevant provisions of the conventions and, in some cases, the principal codes, guidelines, etc. In appropriate cases, the recommendations may incorporate further requirements, which have been found to be useful or necessary in the light of experience gained in the application of the previous provisions. In other cases, the recommendations clarify various questions, which arise in connection specific measures and thereby ensure their uniform interpretation and application in all countries. 4.4.5 DUMPING AT SEA In addition to other aspects of marine pollution prevention, IMO also carties out Secretariat functions in connection with the Convention on the Prevention of Marine Pollution by Dumping of Wastes and Other Matter. This Convention, now called the London Convention, was adopted in 1972 at a conference held under the auspices of the United Kingdom. It entered into force in 1975. ical 4s Troportaionof Choma i Bulk 4The Convention controls and regulates on a global level the disposal at sea of wastes and other material of any kind (including ships and platforms). The disposal of certain substances which from the environmental point of view are known to be particularly harmful (such as organ halogen compounds, mercury, cadmium, plastics, mineral oils and radioactive wastes) is prohibited. The Convention also contains specific regulations concerning the dumping of several other materials, which may present a risk to the marine environment and human health. In addition, it bans the incineration of wastes on board ships. 4.1.6 How it works The International Maritime Organisation works through a number of specialist committees and sub-committees. All these bodies are composed of representatives of Member States who discharge their functions with the assistance and advice of appropriate bodies of the United Nations or the specialised agencies, as well as international governmental and non-governmental organisations with which formal relationships have been established. Formal arrangements for co-operation have been established with more than 30 intergovernmental organisations, while nearly 50 non-governmental, international organisations have been granted consultative status to participate in the work of various bodies in an observer capacity. These organisations represent a wide spectrum of maritime, legal and environmental interests and they contribute to the work of the various organs and committees through the provision of information, documentation and expert advice. However, none of these organisations has a vote. 44.7 THE FUTURE Over the years, IMO has continually evolved to meet changing conditions and requirements. In its early days, it concentrated on formulating international conventions and codes. Today, however, IMO is just as concerned to ensure that the conventions, codes and other instruments already adopted are effectively enforced and implemented. There is significant evidence that IMO measures have already proved beneficial in many areas. Oil pollution of the sea, for example, is less of a threat now than it was 20 years ago and the number of collisions between ships has been greatly reduced in areas where IMO-approved traffic separation schemes have been introduced. But because of economic factors, the average age of the world's ships has risen steadily over the same period and statistics show that old ships have more accidents than young ones. The fleets of the traditional maritime countries - which tend to have good safety records - have declined, while many of the flags that are growing most rapidly have relatively poor records. As a result, nobody can afford to be complacent and IMO is concentrating not only on better implementation but also on improving such factors as management and training, All the evidence shows that most accidents happen because people do not obey the regulations, not because the regulations are themselves defective. ical 4s Troportaionof Choma i Bulk 5BULK CHEMICAL CODES The purpose of this section is to familiarise with the IMO Bulk Chemical Code, their purpose philosophy, layout and application. The purpose of the IMO Bulk Chemical Code for Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk (BCH Code) is to provide an international standard for the safe carriage of dangerous and noxious chemicals in bulk by prescribing the constructional features of ships, regardless of their tonnage, involved in such carriage and the equipment they should carry so as to minimise the risk to the ship, to its crew and to the environment, having regard to the nature of the products involved The basic philosophy is to assign to each chemical tanker one of the ship types according to the degree of hazards of the products carried by such ship. Each of the products may have one or more hazard properties, which include flammability, toxicity and reactivity as well as the hazard they may present to the environment if accidentally released ‘Throughout the development of the Code it was recognised that it must be based upon sound naval architectural and engineering principles and the best understanding available as to the hazards 4.24 THEBCH Cope Under MARPOL 73/78 chemical tankers constructed before 1 July 1986 must comply with the provisions of the Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk (BCH Code). Under SOLAS 74 the BCH Code remains as a recommendation. 4.2.2 THEIBC Cove (On 5 December 1985, by resolution MEPC. 19(22), the IBC Code was extended by the Marine Environment Protection Committee (MEPC) to cover marine pollution aspects for the implementation of Annex II of the International Convention for the Prevention of Pollution from Ships, 1973, as modified by the protocol of 1978 relating thereto (MARPOL 73/78). Under provisions of regulation 13 of Annex II of MARPOL. 73/78, chemical tankers constructed on or after 1 July 1986 must comply with the provisions of the IBC Code. The layout of the Code is in line with the International Code for the Construction and Equipment of Ships Carrying Liquefied Gases in Bulk (IGC Code), adopted by the Maritime Safety Committee at its forty-eight session. Gas carriers may also carry in bulk liquid chemicals covered by this Code, as prescribed in the IGC Code. 4.2.3 NEW sHiP— EXISTING SHIP - New ship means a ship constructed on or after 1 July 1986 - Existing ship means a ship that is not a new ship ical 4s Troportaionof Choma i Bulk ‘4.2.4 EXTRACT FROM THE IBC CoE Chapter 1 1.4 Application SEER Gea SSA RS SESS STEER TNO ScD ACETAL FELCH 4.2.4 Fire hazard, defned by flashpoint, exolosiverfiammabilty limts/range and autoignition temperature ‘of the chemical 1.2.2 Health hazard, defined by: 1 corrosive effects on the skin inthe liquid state: 2 acute toxic effect, taking nto account values of LDso (oral): a dase which is lethal to 60% of the test subjects when administered oraly LLDss (dermal): a dose whieh is lethal to 50% ofthe test subjects when administered tothe skin L.Gsp (inhalation): the concentration which is lethal by inhalation to 50% ofthe test subjects; or 3 Other health effects such as carcinogenicty and sensitization.ee 1.23 Reactivty hazard, defined by reactivity 424 4 with water 125 2 wither 3 with other products: or 4 ofthe product itso (e.9 polymerization) 1.24 Marine polluion hazard, as defines by: 125 2 128 2 lack of ready biodogradbilly 12.7 8 acute toxelty to aquatic organisms: 12.8 A chronic toxicity to aquatic organisms: 1.2.9 5 long-term human health effects and {5 physieal properties resulting in the product floating or sinking and so adversely affecting marine lite 13° Definitions ‘The following definitions apply unless expressly provided otherwise. (Addkional definitions are given in individual chapters) 1.3.1 Accommodation spaces are those spaces used for public spaces, corridors, lavatories, cabins, offices, hospitals, cinemas, games and hobbies rooms, barber shops, paniries containing no ‘cooking appliances and similar spaces. Public spaces are those prions of the accommodation ‘spaces which are used for hal’, dining rooms, lounges and similar permanently enciosed spaces. 4.3.2 Administration means the Government of the State whose flag the ship is ented to fly. For ‘Administration (Port) see Port Administration 4.3.3 Anniversary date means the day and the month of each year which will corespond to the date of ‘expiry ofthe International Cerificate of Finess for the Carriage of Dangerous Chemicals in Bulk. 1.34 Bolling point is the temperature at which a product exhibits a vapour pressure equal to the atmospheric pressure. 1.3.5 Broaath (B) means the maximum breadth ofthe ship, measured amidships to the moulded Ine ofthe ‘ame ina ship with @ metal shell and tothe outer surface ofthe hula ship with a shell of any other material. The breadth (B) shall be measured in metres. 1.36 Cargo area is that part of the ship that contains cargo tanks, slop tanks, cargo pump-rooms including pump-rooms, cofferdams, ballast or void spaces adjacent to cargo tanks or slop tanks ‘and also deck areas throughout the entire length and breaclh ofthe part af the ship over the above- mentioned spaces, Where independent tanks are installed in hold spaces, colferdams, ballast or void spaces al the after end of the aftermost hold space or al the forward end of the forward-most hold space are excluded from the cargo area 1.3.7 Cargo pump-room is @ space containing pumps and their accessories for the handling of the products covered by the Code. 1.3.8 Cargo service spaces are spaces within the cargo area used for workshops, lockers and slo ‘of more than 2 m* in area, used for cargo-nanading equipment. 1.39 Cargo tanks the envelope designed to contain the cargo, ical 4s Troportaionof Choma i Bulk ‘ee > 1.3.10 Chemical tanker's a cargo ship constructed or adapted and used forthe carriage in bulk of any liquid product listed in chapter 17, 1.3.11 Cofferdam isthe isolating space between two adjacent steel bulkheads or decks. This space may be avoid space or a ballast space. 4.3.12 Control stations are those spaces in which ship's radio or main navigating equipment or the emergency source of power is located or where the fire-recording or fire-control equipment is Ceniralized. This doos not include spacial fre-control equipment which can be most practically located in the cargo area 1.3.13 Dangerous chemicals means any liquid chemicals designated as presenting a safety hazard, based (on the safety orteria for assigning products to chapter 17. 1.3.14 Density is the ratio of the mass to the volume of a product, expressed in terms of klograms per cubic mete. This applies to liquids, gases and vapours. 1.3.18 Explosive/lammabilty limitsirange are the conditions defining the state of fuel-oxidant mixture at ‘which application of an adequately strong extemal igniton source is only just capable of producing ‘fammabilty n a given test apparatus. 1.3.18 Flashpointis the temperature in degrees Celsius at which a product wil give off enough flammable vapour to be ignited. Values given n the Code are those for a “closed-cup test” determined by an approved flashpoint apparatus. 1.3.17 Hold space is the space enclosed by the ship's structure in which an independent cargo tank is 1.3.18 Independent means that a piping or venting system, for example, isin no way connected to another system and that there are no provisions availabe for the potertial connection to other systems. 1.3.18 Length () means 96% ofthe total length on a waterine at 85% of the least mouided depth measured from the lop ofthe keel, or the length trom the focesie of the slam to the axis of the rudder stock on that waterline, if that be greater. In ships designed with a rake of keel, the walerine on which this length is measured shall be parallel to the designed waterline. The length (L) shall be measured in metres. 1.3.20 Machinery spaces of category A are those spaces and trunks to such spaces which contain: 1. Intemal-combustion machinery used for main propulsion; or 2 internal-combustion machinery used for purposes other than main propulsion where such machinery has inthe aggregate a total power output of not less than 375 KW; or 3. any oiMired boiler or ol fuel unit or any olfired equipment other than boilers, such as inert gas generators, incinerators, ete 1.3.21 Machinery spaces are all machinery spaces of category A and all other spaces containing propeling ‘machinery, Bolers, oll fuel units, steam and internal-combustion engines, qenerators and maior lactical machinery, ail filing station, refrigerating, slablizing, ventilation and air-conditioning ‘machinery, and similar spaces, and trunks to such spaces. 13.22 1.9.23 Noxious Liquid Substance means any substance indicated in the Pollution Category column of Chapters 17 or 18 ofthe Intemational Bulk Chemical Code, or the current MEPC.2/Cirular or provisionally assessed under the provisions of regulation 8.3 of MARPOL Annex il as falling into ealegories X, ¥, or Z 1.3.24 Oil fuel unit isthe equipment used forthe preparation of fuel for delivery to an alfred boiler, or equipment used for the preparation for delivery of healed oi to an internak-combustion engine and includes any oll pressure pumps, fiters and heaters dealing with oll a a gauge pressure of more than o1eM 1.3.25 Organizationis the Intemational Martime Organization (IMO), ical 4s Troportaionof Choma i Bulk °ee > 13.27 1.3.28 1.3.29 1.3.30 1aat 13.32 13.93 13.34 13.8 13.368 Port Administration means the appropriate authorty of the country in the port of which the ship is, loading or unloading, Products is the collective term used to cover both Noxious Liquid Substances and Dangerous Chemicals ‘Pump-roomis a space, located in the cargo area, conlaining pumps and their accessories for the handling of ballast and oil ful Recognized standards are applicable Intemational or national standards acceptable to the ‘Administration or standards laid down and maintained by an arganization which complies with the standards adopted by the Organization and whien is recagnized by the Adminstration, Reference temperature isthe temperature al which the vapour pressure of the cargo corresponds lo the set prossure of the pressure-raliof valve. Separate means that @ cargo piping system or cargo vent system, for example, is not connected to ‘another cargo piping or cargo vent system, Service spaces are those spaces used for galleys, pantries containing cooking appliances, lockers, mail and specie rooms, siore-rooms, workshops olher than those forming part of the machinery spaces and similar spaces and trunks to such spaces. ‘SOLAS means the International Convention for the Safety of Life at Sea, 1974, as amended. Vapour pressure is the equilrium pressure of the saluraled vapour above a liquid expressed in pascais (Pa) at @ specified temperature. Void space is an enclosed space In the cargo area external to a cargo tank, other than a hold space, ballast space, ol uel tank, cargo pump-room, pump-roam, or any space in normal use by personnel ical 4s Troportaionof Choma i Bulk 10ANNEX II OF MARPOL 73/78 Regulations for the Control of Pollution by Noxious Liquid Substances in Bulk 4.3.1 REGULATION 1 - DEFINITIONS For the purposes of this Annex: 7 Anniversary date means the day and the month of each year which will correspond to the date of expiry of the Intemational Pollution Prevention Certificate for the Carriage of Noxious Liquid Substances in Bulk. 2 Associated piping means the pipeline from the suction point in a cargo tank to the shore connection used for unloading the cargo and includes all ship’s piping, pumps and filters which are in open connection with the cargo unloading line. 3 Ballast water Clean ballast means ballast water carried in a tank which, since it was last used to carry a cargo containing a substance in category X, Y or Z, has been thoroughly cleaned and the residues resulting there from have been discharged and the tank emptied in accordance with the appropriate requirements of this Annex. Segregated ballast means ballast water introduced into a tank permanently allocated to the carriage of ballast or cargoes other than oil or noxious liquid substances as variously defined in the Annexes of the present Convention, and which is completely separated from the cargo and oil fuel system. 4 Chemical Codes Bulk Chemical Code means the Code for the Construction and Equipment of Ships carrying Dangerous Chemicals in Bulk adopted by the Marine Environment Protection Committee of the Organization by resolution MEPC.20(22), as amended by the Organization, provided that such amendments are adopted and brought into force in accordance with the provisions of article 16 of the present Convention concerning amendment procedures applicable to an appendix to an Annex. International Bulk Chemical Code means the International Code for the Construction and Equipment of Ships Carrying Dangerous Chemicals in Bulk adopted by the Marine Environment Protection Committee of the Organization by resolution MEPC. 19(22), as amended by the Organization, provided that such amendments are adopted and brought into force in accordance with the provisions of article 16 of the present Convention conceming amendment procedures applicable to an appendix to an Annex. 5 Depth of water means the charted depth. 6 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 ical 4s Troportaionof Choma i Bulk wof the sea as is reasonable and practicable. 7 Liquid substances are those having a vapour pressure not exceeding 0.28 MPa absolute at a temperature of 37.8. 8 Manual means Procedures and Arrangements Manual in accordance with the ‘model given in appendix 6 of this Annex. 9 Nearest land. The term “from the nearest land” means from the baseline from which the territorial sea in question is established in accordance with international law, except that, for the purposes of the present Convention “from the nearest land” off the north-eastem coast of Australia shall mean from the line drawn from a point on the coast of Australia in: latitude 1100' S, longitude 14208" E to a point in latitude 10°35’ S, longitude 14155’ E, thence to a point latitude 1000’ S, longitude 142° 00" thence to a point latitude 09°10' S, longitude 143° 52° thence to a point latitude 0900’ S, longitude 144° 30° thence to a point latitude 10°41’ S, longitude 145° 00° thence to a point latitude 13°00’ S, longitude 145° 00" thence to a point latitude 1500’ S, longitude 146° 00" thence to a point latitude 1730' S, longitude 147° 00’ thence to a point latitude 2100'S, longitude 152° 55’ thence to a point latitude 2430' S, longitude 154° 00’ thence to a point on the coast of Australia in latitude 24%2' S, longitude 15315’ E. 10 Noxious liquid substance means any substance indicated in the Pollution Category column of chapter 17 or 18 of the International Bulk Chemical Code or provisionally assessed under the provisions of regulation 6.3 as falling into category X, YorZ. moammmmmmm 11 ppm means mi/m3. 12 Residue means any noxious liquid substance which remains for disposal. 13 Residue/water mixture means residue to which water has been added for any purpose (e.g. tank cleaning, ballasting, bilge slops). 74 Ship construction 14.1 Ship constructed means a ship the keel of which is laid or which is at a similar stage of construction. A ship converted to a chemical tanker, irrespective of the date of construction, shall be treated as a chemical tanker constructed on the date on which such conversion commenced. This conversion provision shall not apply to the ‘modification of a ship which complies with all of the following conditions: 1 the ship is constructed before 1 July 1986; and 2 the ship is certified under the Bulk Chemical Code to carry only those products identified by the Code as substances with pollution hazards only. ical 4s Troportaionof Choma i Bulk 214.2. Similar stage of construction means the stage at which: 1 construction identifiable with a specific ship begins; and 2 assembly of that ship has commenced comprising at least 50 tonnes or one per cent of the estimated mass of all structural ‘material, whichever is less. 16 Solidifying/non-solidifying 15.1 Solidifying substance means a noxious liquid substance which: 1 in the case of a substance with a melting point of less than 15°C, is at a temperature of less than °C above its melting point at the time of unloading; or 2 inthe case of a substance with a melting point of equal to or greater than 15°C, is at a temperature of less than 10 above its ‘melting point at the time of unloading. 15.2 Non-solidifying substance means a noxious liquid substance, which is not a solidifying substance. 16 Tanker 16.1 Chemical tanker means a ship constructed or adapted for the carriage in bulk of any liquid product listed in chapter 17 of the International Bulk Chemical Code. 16.2NLS tanker means a ship constructed or adapted to carry a cargo of noxious liquid substances in bulk and includes an “oil tanker” as defined in Annex | of the present Convention when certified to carry a cargo or part cargo of noxious liquid substances in bulk, 17 Viscosity 17.1 High-viscosity substance means a noxious liquid substance in category X or Y with a viscosity equal to or greater than 50 mPars at the unloading temperature. 17.2 Low-viscosity substance means a noxious liquid substance which is not a high- viscosity substance. ical 4s Troportaionof Choma i Bulk 14.3.2 REGULATION 2 - APPLICATION 1 Unless expressly provided otherwise, the provisions of this Annex shall apply to all ships certified to carry noxious liquid substances in bulk. 2 Where a cargo subject to the provisions of Annex | of the present Convention is carried in a cargo space of an NLS tanker, the appropriate requirements of Annex | of the present Convention shall also apply. 4.3.3. REGULATION 4 - EXEMPTIONS 1 With respect to amendments to carriage requirements due to the upgrading of the categorization of a substance, the following shall apply: a where an amendment to this Annex and the International Bulk Chemical Code and Bulk Chemical Code involves changes to the structure or equipment and fittings due to the upgrading of the requirements for the carriage of certain substances, the Administration may modify or delay for a specified period the application of such an amendment to ships constructed before the date of entry into force of that amendment, if the immediate application of such an amendment is considered unreasonable or impracticable. Such relaxation shall be determined with respect to each substance; the Administration allowing a relaxation of the application of an amendment under this paragraph shall submit f0 the organization a report giving details of the ship or ships concemed, the cargoes certified to carry, the trade in which each ship is engaged and the Justification for the relaxation, for circulation to the Parties to the ‘Convention for their information and appropriate action, if any, and reflect the exemption on the Certificate as referred to in regulation 7 or 9 of this Annex; Notwithstanding the above, an Administration may exempt ships from the carriage requirements under regulation 11 for ships certified to cary individually identified vegetable oils identified by the relevant footnote in chapter 17 of the IBC Code, provided the ship complies with the following conditions: 3.1. subject to this regulation, the NLS tanker shall meet all requirements for ship type 3 as identified in the IBC Code except for cargo tank location; 3.2 under this regulation, cargo tanks shall be located at the following distances inboard. The entire cargo tank length shall be protected by ballast tanks or spaces other than tanks that carry oil as follows: -3.2.1. wing tanks or spaces shail be arranged such that cargo tanks are located inboard of the moulded line of the side shell plating nowhere less than 760 mm; -3.2.2. double bottom tanks or spaces shail be arranged such Troportaionof Choma i Bulk Mwthat the distance between the bottom of the cargo tanks and the moulded line of the bottom shell plating measured at right angles to the bottom shell plating is not less than B/15 (m) or 2.0 m at the centreline, whichever is the lesser. The minimum distance shall be 1.0 m; 3.3 the relevant certificate shall indicate the exemption granted. 2 Subject to the provisions of paragraph 3 of this regulation, the provisions of regulation 12.1 need not apply to a ship constructed before 1 July 1986 which is engaged in restricted voyages as determined by the Administration between: 1 ports or terminals within a State Party to the present Convention; or 2 ports or terminals of States Parties to the present Convention. 3 The provisions of paragraph 2 of this regulation shall only apply to a ship constructed before 1 July 1986 if: 1 each time a tank containing category X, Y or Z substances or mixtures is to be washed or ballasted, the tank is washed in accordance with a prewash procedure approved by the Administration in compliance with appendix 6 of this Annex, and the tank washings are discharged to a reception facility; .2 subsequent washings or ballast water are discharged to a reception facility or at sea in accordance with other provisions of this Annex; 3 the adequacy of the reception facilities at the ports or terminals referred to above, for the purpose of this paragraph, is approved by the Governments of the States Parties to the present Convention within which such ports or terminals are situated; 4 in the case of ships engaged in voyages to ports or terminals under the jurisdiction of other States Parties to the present Convention, the Administration communicates to the Organization, for circulation to the Parties to the Convention, particulars of the exemption, for their information and appropriate action, if any; and 5 the certificate required under this Annex is endorsed to the effect that the ship is solely engaged in such restricted voyages. 4 For a ship whose constructional and operational features are such that ballasting of cargo tanks is not required and cargo tank washing is only required for repair or dry- docking, the Administration may allow exemption from the provisions of regulation 12, provided that all of the following conditions are complied with: 1 the design, construction and equipment of the ship are approved by the Administration, having regard fo the service for which it is intended; 2 any effluent from tank washings which may be carried out before a repair or dry-docking is discharged to a reception facility, the adequacy of which is ascertained by the Administration; 3 the certificate required under this Annex indicates: 3.1 that each cargo tank is certified for the carriage of a restricted number of substances which are comparable and can be ical 4s Troportaionof Choma i Bulk 1543.4 carried alternately in the same tank without intermediate cleaning; and 3.2 the particulars of the exemption; the ship carries a Manual approved by the Administration; and in the case of ships engaged in voyages to ports or terminals under the jurisdiction of other States Parties to the present Convention, the ‘Administration communicates to the organization, for circulation to the Parties to the Convention, particulars of the exemption, for their information and appropriate action, if any. REGULATION 6 - CATEGORIZATION AND LISTING OF NOXIOUS LIQUID SUBSTANCES AND OTHER SUBSTANCES 1 For the purpose of the regulations of this Annex, noxious liquid substances shall be divided into four categories as follows: a Category X: 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 resources or human health and, therefore, justify the prohibition of the discharge into the marine environment; Category Y: 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; Category Z: 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; Other substances: Substances indicated as OS (Other substances) in the pollution category column of chapter 18 of the International Bulk Chemical Code which have been evaluated and found to fall outside category X, Y or Z as defined in requlation 6.1 of this Annex because they are, at present, considered to present no harm to marine resources, human health, amenities or other legitimate uses of the sea when discharged into the sea from tank cleaning or deballasting ‘operations. The discharge of bilge or ballast water or other residues or mixtures containing only substances referred to as “Other Substances” shail not be subject to any requirements of the Annex. 2 Guidelines for use in the categorization of noxious liquid substances are given in appendix 1 to this Annex. 3 Where it is proposed to carry a liquid substance in bulk which has not been ical 4s Troportaionof Choma i Bulk 6categorized under paragraph 1 of this regulation, the Governments of Parties to the Convention involved in the proposed operation shail establish and agree on a provisional assessment for the proposed operation on the basis of the guidelines referred to in paragraph 2 of this regulation. Until full agreement among the Governments involved has been reached, the substance shall not be carried. As soon as possible, but not later than 30 days after the agreement has been reached, the Government of the producing or shipping country, initiating the agreement concemed, shall notify the Organization and provide details of the substance and the provisional assessment for annual circulation to all Parties for their information. The Organization shall maintain a register of all such substances and their provisional assessment until such time as the substances are formally included in the IBC Code. 4.3.5 REGULATION 11 - DESIGN, CONSTRUCTION, EQUIPMENT AND OPERATIONS 1 The design, construction, equipment and operation of ships certified to carry noxious liquid substances in bulk identified in chapter 17 of the Intemational Bulk Chemical Code, shall be in compliance with the following provisions to minimize the uncontrolled discharge into the sea of such substances: -1__ the International Bulk Chemical Code when the chemical tanker is constructed on or after 1 July 1986; or the Bulk Chemical Code as referred to in paragraph 1.7.2 of that Code for: 2.1 ships for which the building contract is placed on or after 2 November 1973 but constructed before 1 July 1986, and which are engaged on voyages to ports or terminals under the Jurisdiction of other States Parties to the Convention; and 2.2 _ ships constructed on or after 1 July 1983 but before 1 July 1986, which are engaged solely on voyages between ports or terminals within the State the flag of which the ship is entitled to fly. 3 The Bulk Chemical Code as referred to in paragraph 1.7.3 of that Code for: 3.1. ships for which the building contract is placed before 2 November 1973 and which are engaged on voyages to ports or terminals under the jurisdiction of other States Parties to the Convention; and 3.2 ships constructed before 1 July 1983 which are solely ‘engaged on voyages between ports or terminals within the State the flag of which the ship is entitled to fly. 2 In respect of ships other than chemical tankers or liquefied gas carriers certified to carry noxious liquid substances in bulk identified in chapter 17 of the International Bulk Chemical Code, the Administration shall establish appropriate measures based on the Guidelines* developed by the Organization in order to ensure that the provisions shall be such as to minimize the uncontrolled discharge into the sea of ical 4s Troportaionof Choma i Bulk rysuch substances. “Reference is made to resolutions A.673 (16), as may be further amended, and MEPC. 148(54). ical 4s Troportaionof Choma i Bulk 184.3.6 REGULATION 12 - PUMPING, PIPING, UNLOADING ARRANGEMENTS AND SLOP TANKS 1 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 category X or ¥ does not retain a quantity of residue in excess of 300 litres in the tank and its associated piping and that each tank certified for the carriage of substances in category Z does not retain a quantity of residue in excess of 900 litres jn the tank and its associated piping. A performance test shall be carried out in accordance with appendix 5 of this Annex. 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 category 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 category 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 this Annex. 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 category X, Y or Z does not retain a quantity of residue in excess of 76 litres in the tank and its associated piping. A performance test shall be carried out in accordance with appendix § of this Annex. 4 Fora ship other than a chemical tanker constructed before 1 January 2007 which cannot meet the requirements for the pumping and piping arrangements for substances in category Z referred to in paragraphs 1 and 2 of this regulation no quantity requirement shall apply. Compliance is deemed to be reached if the tank is emptied to the most practicable extent. 5 Pumping performance tests referred to in paragraphs 1, 2 and 3 of this regulation shall be approved by the Administration. Pumping performance tests shall use water as the test medium. 6 Ships certified to carry substances of category X, Y or Z shall have an underwater discharge outlet (or outlets). 7 For ships constructed before 1 January 2007 and certified to carry substances in category Z an underwater discharge outlet as required under paragraph 6 of this regulation is not mandatory. 8 The underwater discharge outlet (or outlets) shall be located within the cargo area in the vicinity of the turn of the bilge and shall be so arranged as to avoid the re- intake of residue/water mixtures by the ship's seawater intakes. 9 The underwater discharge outlet arrangement shall be such that the residue/water ical 4s Troportaionof Choma i Bulk 19