TANKER OPERATION MANUAL MANUAL NO.: FILE NO.: CONTROL NO.TABLE OF CONTENTS. REVISION LOG CHAPTER 1 - THE CARGO, PETROLEUM & ITS NATURE 1 12 13 PREAMBLE... CLASSIFICATION. 1.2.1 DENSITY & VISCOSITY....... 1.22 EFFECTS OF TEMPERATURE... 123 HAZARDS 1.24 VAPOUR PRESSURE & VOLATILITY 1.25 FLAMMABILITY. 5 12.6 USCG.. OTHER CLASSIFICATION: 1.37 SPIKED... GAS CONCENTRATIONS DURING TANKER OPERATIONS 1.4.1 DENSITY & VAPOUR PRESSURE..... 1.4.1.1. Vapor Conditions of Petroleum Liquid: VOLATILE PETROLEUM. LOADED CARGO TANKS DISCHARGING CARGO TANKS. 1.4.4.1 Formation of Vapor 1.4.5 EMPTY CARGO'TANK: 1.4.5.1 Relationship 1.4.6 TANK CLEANING .. 1.4.7 GAS FREEING... 1.4.8 LOADING CARGO TANKS. 4 148.1 TyplalHycrocarben Content of Vent Gas During Loating of Crode 4.4.82 Cargo Vapor Concentration, Hail Tank Loading . 4.4.8.3 - Cargo Vapor Concentration, Cargo Tank Nearly Full. 4.9 HIGH VAPOUR PRESSURE 4,10 RESIDUAL FUEL OILS. BBR 2 GSSoa ee tt RaS my 1.14 TABLE OF CONTENTS CONT'D 1.4.11 INERT GAS... 1.4.12 COMBUSTION & EXPLOSION, THE TOXIC EFFECTS OF HYDROCARBON GASES.. 1.5.1 INGESTION. 1.5.2 ABSORPTION. 1.5.3 INHALATION. 1.5.4 ASPHYXIA, ANAESTHESIA & NARCOSK AROMATIC HYDROCARBON! HYDROGEN ae MERCAPTAN; PYROPHORIC Siow SULPHIDE CATHODIC PROTECTION, SHIP/SHORE & SHIP/SHIP ELECTRICAL CURRENTS....24 1.13.1 ELECTRICAL FLOW WHILST VESSEL 1.13.1.1 Flow of Electrostatic Charge 1.13.2 JETTY CATHODIC PROTECTION. 1.3.2.1 Cathodic Protection of Jetty .. “1.13.3. SHIP & JETTY CATHODIC PROTECTION 1.13.33 Insulated Flange Detal... 4.13.4 BONDING WIRES... (CRUDE OIL REFINING... 4.44.1 FIRST STAGE DISTILLATION... 1.14.11. Refining Process 1, Distillation.. 1.14,2. THERMAL CRACKING 1.14.2.1 Refining Process 2, Thermal Cracking. 1.14.3 CATALYTIC CRACKING... 1.14.34 Refining Process 3, Calalyic Cracking 1.14.4 VACUUM DISTILLATION/VISBREAKING ..... 4.14.4.4 Refining Process 4 & §, Vacuum BreakingiVisbreaking CHAPTER 2- CONSTRUCTION & DESIGN OF THE MODERN TANKER 24 HISTORICAL DEVELOPMENT. 2.1.1 THE FIRST TRANSPORTATION OF OIL BY SEA...TABLE OF CONTENTS CONT'D 2.1.2 SUMMER TANKS & EXPANSION TRUNKS. 21.2.1 Cross Section of Early Oil Tanker with Summer Tanks. 24.3 TRANSVERSE & LONGITUDINAL FRAMING... z 1.3.1 Compositely Framed Tanker Construction. 3.2 Longitudinally Framed Tanker Construction aa 3 Older Tanker Construction (Combined/Composite System — Longitudinal & Transverse Framing)... 2.1.3.4 Modern Tanker Construction (Longitudinal mee Section) 22 EXISTING, RECENT & MODERN DEVELOPMENTS... 2.2.1 CBT (DEDICATED CLEAN BALLAST TANKS)... 2.2.1.1 Simplified Schematic Representation of CBT, Single Hull 2.22 SBT(SEGREGATED BALLAST TANKS). 222.1 Simplified Schematic Representation of Early SBT Tanker, Single Hull. 2.22.2 — Simplified Schematic Representation of Later SBT Tanker, Single 223 DOUBLE HULLS. 2.23.1 Simpl epres 22.4 MID-DECK, Tenoorans 6a BALANCING... 22.4.1 — Simplified Schematic Representat Hydrostatic Balance Loading...... 23. LAYOUT & DESIGN OF TANKS, DETAILS OF SPECIFIC CONSTRUCTION, SYSTEMS t= & EQUIPMENT... Md 2.3.1 CARGO TANK CONSTRUCTION oe 232 2.3.3 PIPELINE SYSTEMS... 2331 Double Ribg Main Pipeline System, Product Carrier. 2.33.2 VLCC, Free-Flow Syste 2.33.3 Group Cargo Pele § Sysiem _ Patesiar Class CHAPTER 3 - CARGO SYSTEMS & EQUIPMENT 34 MAIN CARGO AND BALLAST PUMPS...32 33 Ses eeu eee ees Seaywrseyr ss" * TABLE OF CONTENTS CONT'D E CENTRIFUGAL PUMPS.. PRINCIPLES OF OPERA PUMP ENERGY, PUMP EFFICIENCY... NET POSITIVE SUCTION HEAD (' CAVITATION 2S ee Eeees &® Nomaens g = : 6 i 2 ‘Stopping the Pump. Changing Cargo Tanks .. 3. Venting the Pumy 3.1.8.5 Ait/Vapour Lock, "Gassed Up" SSSS5N suoverns 3.1.9 LIQUID HAMMER. 3.1.10 PRESSURE SURGE. 3.1.11 PUMPS OPERATING IN PARALLEL STRIPPING SYSTEMS... 3.2.1. CARGO PUMP PRIMING SYSTEMS 1 Steam Ejector. 2 VacStrip and Automatic Unloading Systems. 32.1.3 Prima-vac System. 322 EDUCTORS. 32.3. STRIPPING PUMPS 32.3.1 Reciprocating 3.2.3.2 — Other Stripping Pumps. PIPELINE SYSTEMS, VALVES AND CARGO FLOW CONTROL. 3.3.1 PIPELINE SYSTEMS. 3.3.4.1 Loading. BES 3.3.2 33.23 3.3.24 3.1.3 REMOTE HYDRAULIC CONTROL SYSTEM... INERT GAS SYSTEM (IGS), VENTING AND VAPOUR RECOVERY AND BALANCINGS335 36 37 38 39 3.10 TABLE OF CONTENTS CONT'D 3.4.1 INERT GAS SYSTEM (IGS). 34.1.1 Boiler Uptake Valves. 344.2 Scrubber Tower... 34.1.3. Inert Gas Fans/Biowers. 3414 Oxygen Analyzer.. 3.4.1.5 Temperature Monitor. Inert Gas Delivery Valve, 34.10 34.1.8 3.4.2 DECK MAIN DISTRIBUTION/VENTING SYSTEM 34.21 — Isolating 3422 3.42.3 Mast Riser, Vent Valve, Pressure/Vacuum Valve and Flame (Venting System)... 3424 3425 3426 3427 3428 3.4.3 VAPOUR EMISSION CONTROL... GAUGING EQUIPMENT. 3.5.1 FIXED CARGO FLOAT GAUGING SYSTEM. 3.5.2 OVER FILL ALARM SYSTEM... 3.5.3 FIXED BALLAST AIR PURGE SYSTEM OIL DISCHARGE MONITORING AND CONTROL EQUIPMENT. TANK CLEANING AND CRUDE OIL WASHING SYSTEMS... 3.7.1 FIXED TANK CLEANING MACHINE: 3.7.1.1 Top Mounted Machines. 3.7.1.2 Bottom Mounted Machines. PORTABLE CARGO EQUIPMENT.. 3.8.1 CLOSED ULLAGE SYSTEM... B82 B8s2s 8 83s GAS FREEING FANS... CHAPTER 4 - PRACTICAL OPERATIONS: 44 THE BALLAST PASSAGE.......TABLE OF CONTENTS CONT'D 1 ‘TANK PREPARATION. 2 PURGING. 3 WATER FLUSHING... TANK CLEANING RAS 41.5 GAS FREEING $.1 Isolating Tanks Testing Tank Atmospheres Tank Entry SLOP TANKS AND DECANTING. *MARPOL" and Oil P. Oil Discharge Monitoring and Centro} Discharge of Bottom Water (Decanting). 416 4AT 41842 TABLE OF CONTENTS CONT'D 4.1.8.11 Loading Plan Finalization and Changes. 448.12 Standing Orders . 4.1.9 LOADING PORT PRE-ARRIVAL. 44.9.4 44.92 41.9.3 41.9.4 41.9.5 Cargo Line Preparation. LOADING PORT 42.1. SHIP AND TERMINAL REQUIREMENTS. 422 COMMUNICATIONS..... 423 HOSE CONNECTION... 29 42.3.1 Shipand Terminal Stat. 29 423.2 Ship’ 29. 42.3.3 Manifold Blanks and Presentation Flanges. 30 423.4 30 4235 30 4236 30 4237 34 423.8 31 ee 42.4 TANK GAUGING... ca] zy 4.2.4.1 Surveyors and other Shore Personnel 31) Gauging/inspecting Tanks.. 4 a 32 32 32 a 2 34 34 425 LINE SETTING......... ms en 42.5.1 Manifold Drain, Vacuum Breaker, Pump Room and Unused Valves. 34 42.5.2 Remote Control Hydraulically Operated Valves. 35 4.2.5.3 Inert Gas and Venting Systerns... 35 4254 2 35 7 425.5 35 pe 425.6 36 a 425.7 36 z 428 VESSEL/TERMINAL PRE-OPERA’ SAFETY AND CARGO MEETING.36 5) 4.26.1 Material Safety Data 38 1aeaelUCrCrCrClUC CC COC lCUlUCUCrCrCUClC OrCUC CrUCUC OrClCUlUCU rOCT_ClCUC OCCULT Ur CUr™ 43 427 428 429 42.10 42.14 4242 4.2.43 4.2.14 4.2415 42.16 4247 42.18 THE LOADED PASSAGE... 434 TABLE OF CONTENTS CONT'D 4.2.6.2 ~ Safety ChecklisDeclaration of Inspection. 4.2.6.3 Communications. INITIAL LOADING. SAMPLING... BULK LOADING. LOADING RATES... LOADING PROCEDURES AND CHECKS. 4.2.14.1 Cargo Ullages and Calculations. 4.2.11.2 Equipment and Oil Pollution Monitoring 4211.3 Cargo Gauges “TOPPING OFF". 42.1214 Last Tank to be Loader 42122 Dock Water Density. 4.2.42.3 Reduction of Loading Rate. NOTIFICATION OF REOUCING LOADING RATES AND COMPLETING one HOSE AND PIPELINE DISPLACEMENT! (CHANGING TANKS AND GRADES. BILL OF LADING DENSITYIAPI... AZqT2 Beles inspection. 42.17.3 Ballast Discharge 4.2.17.4 Contaminated Ballast .. AFTER LOADING... 4.2.18.1 Draining 4,2.18.2 _ Disconnecting Hoses... 4.2.18.3 Cargo Gauging and Calculations 4.2.18.4 Sampling... THERMAL EXPANSION AND VENTING 43.14 43.13 preldag Venting 01 "3.1.4 Cargo Expansion Allowance Contraction DISCHARGE PLANNING .....s-ssecesnemsseenrnseee 4.3.3.1 Use of Pumps... viitTABLE OF CONTENTS CONT'D 4.3.3.2 Pumping Warranties. 43.3.3 Ship's Discharge Limitations 4.3.34 Discharge Terminal Restrictions. 4.3.3.5 Pipeline Displacements. 4336 43.37 4.338 43.39 43.310 4.33.11 pbheeeone 4.3.4 THE DISCHARGE PLAN 4.3.4.1 434.2 Final Stripping and Completing the Discharge. 43.5 PRE-ARRIVAL PREPARATION ANO CHECKS... ° 44 DISCHARGE PORT... S Bgeege ge 4.41 PRE-DISCHARGE OPERATIONS. 4.4.1.1 Hose Connection... AAA CARGO TANK ‘GAUGING. AFTER DISCHARG! DRAINING LINES AND HOSE DISCONNECTION CHAPTER 5 - OTHER OPERATIONS 5.1 CARGO HEATING... CARGO HEATING INSTRUCTIONS...62 53 54 55 56 57 TABLE OF CONTENTS CONT'D MONITORING CARGO HEATING.. ‘CARGO HEAT LOSSES LOCALIZED HEATING - CARGO STEAM HEATING SYSTEM ‘STEAM HEATING CONTROL STEAM TRAPS... HEATING COILS. ‘STEAM HEATING COIL OPERATION STRIPPING HEATED CARGOS.. OBQ AND ROB TANK GAUGING. 5.2.1 DETERMINATION OF OBQ AND ROB, TANK INSPECTIONS. 5.22 WATER FINDING AND GASOLINE. ro a Ip SS022G2e &@ sVODRwWEwal® CARGO Et 5.2.8 ROBAND EXTENDED DISCHARGE. ‘SHIP TO SHIP TRANSFER. BUNKERING OPERATIONS INERT GAS OPERATIONS .. $51 SOLAS REQUIREMENTS... 5.5.2 PARTIAL AND COMPLETE FAILURE. 5.5.3 MONITORING AND TESTING CARGO TANK ATMOSPHERES .. 5.5.4 OPTIMUM OXYGEN CONTENT .... P- 5.5.5 PLANNING INERT GAS: OPERATIONS. 5.5.6 TANK PRESSURE/VACUUM.... $5.7 THE MAST RISER AND PRESSURE/VACUUM BREAKE! 5.5.8 MULTI-GRADE CARGOS.... 5.5.9 TANK CLEANING, PURGING AND GAS FREEIN' 5.5.10 TANK ENTRY -ss: 55.11 PRE-OPERATION CHECKS... ih OPERATION OF THE meee, ed ‘SYSTEM.. 6,13 INERT GAS DELIVERY TO DECK.. 55. 14 AUTOMATIC CONTROL. AND MONITORII 5.5.15 STOPPING THE INERT GAS SYSTEM..... TANK INSPECTIONS AND VALVE TESTING ..... 56.1 TANKENTRY... 5.6.2 TANK INSPECTI 5.63 PRESSURE TESTING PIPE PIPELINES AND /ALVES. CRUDE OIL WASHING.......0+-reere — 5.7.1 PRE-OPERATIONAL CHECKG.......... 5.7.1.1 Planning and Notification,58 CHAPTER 6 - DOCUMENTATION 64 62 63 64 CHAPTER 7 - POLLUTION, REGULATION & CONTROL TA 72 WW TABLE OF CONTENTS CONT'D $.7.1.2 Oxygen and Hydrocarbon Gas Melers 5.7.1.3 COW System Inspection 5.7.1.4 COW Pipeline Pressure Testing... 5.7.1.5 COWLine Setting... 5.7.2 COW OPERATION AND MONITORIN' 5.7.2.1 Communications... - 5.7.22 Cargo Tank Atmosphere .. 5.7.2.3 Duty Personnel on Dect 5724 Line Setting... 57.25 Electro-Static 5.7.26 — Opening Valves and Pressurizing the System 5.7.2.7 Monitoring... 5.7.3 FULL, TOP, MIDDLE AND BOTTOM WASHING. 57.3.1 Full Washing 5.7.3.2 Botton Washing. 5.7.3.3 Top and Middle Washing. 5.7.4 ULLAGE GAUGES.. 5.7.5 STRIPPING AND SLOP TANKS. 5.7.6 STOPPING WASHING. 5.7.7 TANK ee AND VERIFICATION OF CRUDE OIL WASHING EFFECTIVENES: 5.7.8 COMPLETING OPERATIONS BALLAST OPERATIONS. DOCUMENTATION REQUIREMENTS. COMPLETING DOCUMENTS ..... DOCUMENT TYPES. 63.1 CHECKLISTS. 63.2 PLANNING Fi 6.3.3. INFORMATION DOCUMENTATIO! 6.3.4 RECORD KEEPING DOCUMENTATIO! COMPLETING AND SIGNING DOCUMENTS ..... THE INTRODUCTION OF SOLAS..... THE FIRST NATIONAL LEGISLATION FOR 1 THE PREVENTION ‘OF POLLUTION OF THE GEA BY Often eeceasncosstcnsis TIONAL LEGISLAT THE MAJOR OIL COMPANIES AND “LOAD O} JOTTSG, OCIMF AND ISGOTT ... ssssesemoeseorser AMENDMENTS TO THE 1954 CONVENTION MARPOL "73. scacssscsessesecesscseooteorevn seen Dara Tay 7714 7.16 TAG TABLE OF CONTENTS CONT'D SOLAS, MARPOL AND STCW AMENDMENTS. THE U.S. AND OPA'90. ISM... IMPLEMENTATION AND PROMULGATION .. THE REGULATIONS 7.15.1 SOLAS ‘74 7.45.2 MARPOL 73/78 7.45.3 PUBLICATION: 7.15.4 ISM 7.15.5 WA‘ 7.15.6 OPA’'90, CALIFORNIA AND WASHINGTON STATES “VESSEL RESPON: PLANS”, FAMILIARITY... CHAPTER 6 - INCIDENTS 84 82 83 84 85 86 87 ‘SHORE/TERMINAL INCIDENTS.. NON CARGO INCIDENTS... ‘CARGO OPERATIONAL PROCEDURES, OIL POLLUTION... ‘CARGO OPERATIONAL PROCEDURES, COMMERCIAL. ‘STRUCTURAL DAMAGE INCIDENTS. EQUIPMENT FAILURE INCIDENTS. CONCLUSION... Onaonan CHAPTER 9 - GLOSSARY OF TERMS. xii| CHAPTER 1 THE CARGO, PETROLEUM & ITS NATURECHAPTER 1 - THE CARGO, PETROLEUM & ITS NATURE 4.4 PREAMBLE In order to better understand the equipment, the operations involved, precautions and lures necessary for the safe carriage of petroleum as a bulk cargo it is beneficial if some of 7 the physical and chemical properties of the cargo are known. This chapter deals with the nature ang- properties of hydrocarbons and the hazards associated with its handling. All of these have influencec the design, construction and operation of oil tankers to varying extents. 3 Further references are made to other manuals and booklets which should be consulted. These include “Post-Fixture Operations", "Regulations & Instructions to Masters & Officers’, "Stay Alive - H,S Kills" “Petroleum Products" and the ICS/OCIMF publication “International Safety Guide for Oil Tankers Terminals (!SGOTT)’ 41.2 CLASSIFICATION Oil is defined as one of various viscous liquids, flammable and insoluble in water. Petroleum is generic term for all hydrocarbon-based oils, from the raw material, crude oil, to thediverse products—— refined from it. - A liquid is almost incompressible, has both mass and volume, hence density (specific gravity) al weight. It is viscous (has a resistance to flow) and expands and contracts with rising and falling temperature respectively. 4.24 DENSITY & VISCOSITY The density of a substance is a measure of its mass per unit volume. It is a measure of the mass quantity of material within a substance and when subjected to the force of gravity, it becomes measure of the heaviness of the substance, i.e., the weight. The relative density or specific gravity, measure at a standard temperature and pressure is the ratio the mass of a volume of the product to the mass of an equal volume of air or water, Le., if substance is liquid, to an equal volume of pure water, if gaseous to an equal volume of air. These properties of a substance when applied to petroleum can indicate certain physical characteris that the liquid will display. The viscosity will also form part of the picture. The viscosity of a liquid ise Measure of its ability to flow. In terms that are more technical, it is a measure of the internal re: — to motion within the liquid or internal friction, In very simple terms, it is a measure of the “thickness” oF “thinness” of a liquid. The two properties of density and viscosity when applied to a liquid and their physical properties Rot be confused when considering the requirements of pumping and transporting petroleum. Gistinetion should also be made between a liquid's viscosity and its pour point. This distinction is” important when considering heating requirements. The combinations of pour point and viscosity will influence any requirements to heat the petroleum for” Pumping and transport. Viscosity In a liquid hydrocarbon is the result of an high asphalt t.whereas a high pour point is the result of an high wax content. A high viscosity or a high pour point will gach increase the need to apply heat to the cargo (o keep it fluid for both transportation and pumping. aliquid may have a high density, but low pour point andlor lew viscosity wil flow easily whereas @ low ‘density, high pour point and/or high viscosity liquid will not. An example of the former may be a light fuel oil, of the latter, vacuum gas oil (VGO). The light fuel oil although dense, has a low viscosity and low pour point. The VGO will require considerable heating to keep it liquid. 1! may have @ pour point temperature in the region of 52°C, Certain crude oils can require heating due to (either or both) high . viscosity and/or high pour point. Examples of these are: Bachaquero Crude Oil out of La Salina, Venezuela - this has a density of about 0.97, a high viscosity of 330 centistoke and a low wax content and pour point of -10°F, Duri Crude from Dumai, Indonesia - this has a density of about 0.92, a high viscosity of 114 centistoke and a high wax content and high pour point of 60°F. i + Tanjung Crude from Indonesia which has a density of about 0.83, a low viscosity of 5 centistoke and a high wax content and high pour point of 104°F, All three crude oils require heating to remain liquid and pumpable. 1.2.2 EFFECTS OF TEMPERATURE Oil by definition is a liquid. As a pure material it will have a solidifying point, this is defined as the temperature at which the liquid will solidify at normal standard pressure when heat is extracted from it. However, since most hydrocarbon oils are not pure, containing many different structures of the hydrocarbon molecule and other impurities, this temperature is very difficult to determine. Therefore, the Pour Point is more commonly used. This is determined as 5°F (2.8°C) above the temperature at which the oil will lose its ability to flow. The liquid ceases to flow and begins to solidify as the wax within the hydrocarbon liquid begins crystallizing out of suspension in the liquid. It begins to form a network structure at approximately the temperature of the pour point which causes the liquid to begin to solidify as the temperature of the liquid falls. « if the temperature of the oil is raised, it will reach a point at which it will give off vapour. This is the boiling point of the liquid. This is also the temperature at standard pressure at which equilibrium is reached between atmospheric pressure and the saturated vapour pressure of the liquid. Further heating of the liquid will increase the vapour boil off, This increases the concentration of hydrocarbon gas in air until a point is reached where the ratio of hydrocarbon gas to air is just sufficient to support and propagate combustion. This point is known as the Lower Flammable (or Explosive) Limit (LFL or LEL). . If @ source of ignition is introduced to the vapour at this point, it will burn. This point is known as the Flash Point of the liquid. However, it will not support continued combustion, as once the initial vapour \s burnt off, insufficient additional vapour will be released to maintain combustion. ith further heating, ie., increased temperature of the liquid, it will reach a point where sufficient | vapour Is liberated to support and maintain combustion. This is known as the Fire or Combustion or Burning Point. In oils with flash points above 100°C this point, may be between 5 and 20°C higher than the flashpoint. However, in oils with a fiash point below 100°C the flash point and fire point are almost the same. 2Further heating of the liquid, without the introduction of a source of ignition, will continue to liberat more vapour from the liquid until the ratio of hydrocarbon gases to air reaches a point where th mixture will contain too much hydrocarbon gas and too little oxygen to support and propagat combustion. This is known as the Upper Flammable (or Explosive) Limit (UFL or UEL). - Further heating of the liquid will eventually cause it to ignite itself, This point is known eilher as th Ignition, Spontaneous Ignition, or Auto Ignition Temperature. - 1.2.3 HAZARDS The two main specific hazards, which arise from the nature of the cargo, are of Flammability an Toxicity. They both derive essentially from the vapours liberated from the liquid. Although the flammable property of hydracarbon oil vapours is its greatest benefit in the modern age when usec under controlied conditions, any use or occurrence of vapor ignition under uncontrolled conditions cat have disastrous consequences. The other principle hazard arises when the toxic vapours are inhaled Ingestion of the liquid and skin contact can also present a significant hazard. 1.2.4 VAPOUR PRESSURE & VOLATILITY Hydrocarbon oils are mostly a mixture of a wide fange of hydrocarbon compounds. The boiling points o; these compounds vary between as low as -162°C. up to and in excess of +400°C. The volatility of < hydrocarbon-based liquid, which is to say the ease with which it will turn into a vapour, depends upor. the quantities of the compounds with boiling points nearer the lower end of this range of temperature. These are usually compounds which exist in a gaseous state at normal almospheric pressure and include Methane, Ethane, Propane and Butane, etc, The volatilities of ois are characterized by their Vapour Pressure. The vapour pressure of an oil is important in respect of the flammability hazard associated with the evolution of gases, It is also a factor in determining how easily a liquid can be pumped, This is discussed in Chapter 3, Section 3.1, concerning pumps. When an oil is transferred to a container free of gases, it will immediately begin to vaporise, liberating 98s into the space above the liquid level. However as more gas is liberated there Is a tendency for the 988 to re-dissolve into the liquid. This will continue until a balance is reached where a certain amount of gas will evenly occupy the space above the liquid. The pressure exerted by the evolved gas on the liquid is known as the vapour pressure of the liquid, The vapour pressure of a pure compound is dependent only on its temperature. The vapour pressure of @ mixture is dependent upon its constituents and the space available for gas evolution from the liquid as Well as ils temperature. The True Vapour Pressure of a liquid is the pressure exerted on the liquid when the ratio of gas to liquid is effectively zero at a specified temperature. Therefore, it is seen that as the temperature of a ‘iquid is increased, then its vapour pressure also increases. If the vapour pressure of a liquid exceeds atmospheric pressure, then the liquid will boil. The True Vapour Pressure of a liquid is a good measure of its ability to evolve gas. However, it is extremely difficult to measure without detailed knowledge of the constituents of the liquid. In crude oils it ‘an be estimated from the stabilization conditions and allowing for temperature changes andcomposition. In petroleum products it can be derived from what is known as the Reid Vapour Pressure (RVP). the Reid Vapour Pressure of a liquid is simply measured by standard apparatus in which a liquid is witroduced into a container at atmospheric pressure. The volume of liquid in the container is carefully controlled to occupy one fifth of the total volume of the container. The container is then sealed and heated in a water bath until a temperature of )"F) is reached and stabilized, The container is then agitated to ensure an even dispersal of gas within the container ullage space. A pressure gauge attached to the container will indicate the rise in pressure due {o the vaporization of the liquid. This, reading is the Reid Vapour Pressure of the liquid. The RVP is of litle value or indication of the abliity of a liquid to evolve gases in specific situations, but is useful for comparison purposes of the volatility of the wide range of petroleum compounds. 1.2.5 FLAMMABILITY Petroleum is considered an inflammable liquid. Nevertheless, it is not the liquid that bums, but the gas ‘evolved from the liquid. Therefore as previously discussed certain conditions must be met before the petroleum will ignite or burn, In this way the vapour pressure of the liquid is seen as a measure of the liquid's volatility and hence flammability, This is commonly used to classify petroleum liquids. The basic consideration in classifying petroleum liquids by flammability is whether or not a ges/ air -ixture within the range of flammable equilibrium can be formed in the space above the liquid when the {iQuid is at ambient temperature. If the flashpoint of the liquid is below the ambient temperature then the liquid has a particular hazard. Firstly, it Is easier to understand the classification if the definitions of combustible, inflammable, and volatile are understood with respect to petroleum liquids. Combustible - capable of burning. inflammable - easily set on fire (this word is the same as flammable). Volatile. = evaporating rapidly — Therefore combustible liquids are classified as either volatile/non-volatile or flammable (inflammable). Most of the world uses the broad classification of liquids being either volatile or non- ~slatile, whereas the USCG categorize the liquids as flammable and combustible, which are further ubdivided into a further five alphabetic grades - A, B, C, D and E. SOLAS regulations also classify flammable liquids. Volatile - Flashpoint below 60°C, as determined by the closed cup method of testing. Non-volatile - Flashpoint of 60°C or above, as determined by the closed cup method of testing. : > Volatile liquids tend to produce balanced gas/air mixtures either within the flammable range or above the upper flammable limit, at normal ambient temperatures, Examples of the former are Kerosene and » Jel Fuels, of the latter are Crude Oils and Gasolines. Non-volatile liquids produce balanced gas/air mixtures below the tower tammabie. ft, at normal ambient temperatures. Examples of these are Heavy Gas Oils, Diesel Oils and Residual Fuel Oils.Tlashpoint or above, or if the characteristics of a cargo are unknown it should be treated um all the required precautions and safety measures. An example is the residu )- fuel oils carried either as a fuel or cargo. Due to Capabilify to produce light hydrocarbons, the can produce vapour compositions above the liquid, which may lie within the flammable range. This cer occut even if the liquid temperature is below its flash point. As such, they should always be treated ¢~ volatile and all the required precautions and safety measures must be taken. Further discussion of th can be found in this chapter, see Section 1.4.10. r The closed cup method of testing is an industry standard test in which a sample of the liquid is heate, =in a closed or covered container, A flame or source of ignition is repeatedly and momentarily applied t™ the surface of the liquid whilst it is being heated. The flashpoint is the lowest liquid temperature at whic the flame or ignition source initiates a flash of flame across the surface of the liquid. There is also ap open cup test where the container of the liquid is open and gives a higher flashpoint by the greater los of gas to atmosphere. This latter témperature fends to’ be about_6°c higher than tie closed cup tt | temperature, — The two industry standard tests for flashpoint and Reid Vapour Pressure iridicate the volatility flammability of the liquid, 1.2.6 uscG In these regulations a flammable liquid_means any liquid which gives off flammable vapours (a%7= determined from an open cup tester, as used for a test of burning oils) at or below a 80°F (26.67°C). Flammable liquids are referred to by the following grades: GradeA - Any flammable liquid having a Reid Vapour Pressure of 14 pounds or more. GradeB - Any flammable liquid having a Reid Vapour Pressure under 14 pounds and over 8"/, pounds. GradeC - Any flammable liquid having a Reid Vapour Pressure of 8% pounds of less and a flashpoint of 80°F or below. A combustible liquid means any liquid having a flashpoint above 80°F (as determined from an open cuj test, as used for a test of burning oils). Combustible liquids are referred to by the following grades: GradeD - Any combustible liquid having a flashpoint below 150°F and above 80°F. GradeE - Any combustible liquid having a flashpoint of 150°F, or above. 1.3. OTHER CLASSIFICATION The principle cargo carried by Company vessels is crude oil and this can be separately classified on the bese of its hydrocarbon type, sulphur content, boiling point, vapour pressure, heating and 2s ‘Our oF sweet. Crude oil is @ raw material, also known as Petroleum, Rock or Mineral Oil and as Naphtha. This Name should not be confused with the misnamed petroleum oradiict "Nanhthalens® cammanhs satare=:to as Naphtha, Crude oil is composed mainly of many different kinds of hydrocarbons with very small | amounts of nitrogen, sulphur and oxygen compounds ‘and metals. It is the varying amount of all of these compounds contained in crude oils that give rise to the many diverse crude oils found throughout * jhe world. * 4.3.14 HYDROCARBON TYPES There are four basic types of hydrocarbons under which crude oils can be classified. These are: 1) Paraffin Hydrocarbons ‘These are one of the main components of the hydrocarbon groups that make up crude oil. They are the hydrocarbons of the Methane series and ae the properties of i density and low viscosity, but commonly with a high wax content. 2) Naphthene Hydrocarbons These are the other main group of hydrocarbons found in crude oil. They display the property of heavier density than the Paraffin Hydrocarbons and greater viscosity. 3) Olefin Hydrocarbons Raw crude oil contains few Olefin Hydrocarbons. They are mainly produced in the refining process ~ and are hydrocarbons of the Ethane series. They are akin to the Paraffin carer group, 4) Aromatic Hydrocarbons Few Aromatic Hydrocarbons are contained in raw crude oil. They are similar to Naphthene Hydrocarbons and Include Benzene, Toluene end Ayiens, These represent the grestest Health tisk of all the hydracarbon grolips_and qund 2 asolines ai Reformates, Naphthas, Special Bolling Pant Sonents (5 aes White Spirits and Crude Oils. This is discussed later under the toxic effects of hydrocarbons. 1.3.2 SULPHUR CONTENT : “Aany crude oils have a high sulphur content which is generally undesirable in the refining process due To the deterioration of Product and the high risk of air pollution, One of the more dangerous compounds of sulphur in crude oils is Hydrogen Sulphide. This may be present in relatively large percentages of between 0.1 and 5% in any given cargo. The quantity in crude oil is sometimes reduced by a stabilization process before transportation. However, high levels of ‘hydrogen sulphide are found in some crude oils of this group. The dangers of hydrogen sulphide are discussed later in the section, see . Section 1.7, concerning the 8 effects of hydrogen sulphide and in the booklet found on board “Stay Alive H2S Kills".1.3.3 BOILING POINT . Crude oils are also classified by boiling point. Petroleum products are refined from the raw cruge oil | using the different boiling points of the many components of crude oil, Light many _low_bailing—point hydrocarbons, whereas the heavier crude oils tend to contain a reat acavier crude ols tend to contain a great proportion of the higher boiling point hydro * 1.3.4 VAPOUR PRESSURE Another classification of crude oils is the vapour pressure, being either high or low, Crude oils terme as Heh Vapour Pressure crude oils contain many low boiling point hydrocarbons, with high volatilit al igh vapor . This type of crude oil has the potential for high cargo loss due to vape emission and for problems associated with pumping. f 1.3.5 POUR POINT High pour point is another classification of petroleum. High paraffin wax content and/or high viscosit: due to asphalt content requires the oil to be heated in excess of ambient temperatures to keep th: petroleum liquid for transportation and pumping. 1.3.6 SWEET/SOUR - The classification of petroleum as Sweet or Sour is made upon the percentage of sulphur fs within the petroleum, When a petroleum contains a igh percentage (more than 1%) of sulphur Ceiecudieare cae Particularly of hydrogen sulphide (H,S), they are referred to as ‘Sour’ crudes, due the Pungent odor of the liquid. Where crude oils contain less than ‘1% or’ negiigible traces of sulphur compounds, they are referred to as Sweet. 1.3.7 SPIKED Spiked Crude is crude oil, which is spiked or enriched with either naphthalene or butane to stabilize the crude oil and/or other petroleum products. This may be done before being loaded or by onboard commingling. Spiked crudes must always be treated as volatile. 1.4 GAS CONCENTRATIONS DURING TANKER OPERATIONS Due to the introduction of inert gas which provides a blanket cover to inhibit the chemical reaction of Combustion even when a source of ignition Is introduced, the knowledge of gas concentrations and Compositions within the cargo tank spaces are in danger of being ignored. This knowledge is important in the event of the failure of the inert gas system, of in the event of an incident where cargo oil ‘and gas 8re released from its containment within the cargo tanks, or the ingress of air is permitted Into the cargo Spaces. This knowledge is particularly relevant when carrying residual fuel oils as bunkers where the tanks are not protected by inert gas. For the sake of argument, the following paragraphs assume that fresh air is the medium in the cargo tank space as opposed to inert gas. The use of inert gas is not considered here, in order to highlight the angers involved in cargo operations without the use of inert gas. In this way the benefits derived from———— the use of inert gas are more obviously seen. It must be remembered that for all cargo operations the use of inert gas Is obligatory. 4.41 DENSITY & VAPOUR PRESSURE ‘The density of hydrocarbon vapours relative to air is also extremely important when assessing the flammable risks of hydrocarbon vapours. usuall fan. ). This means thal they will tend to fall or migrate below air (and inert gas) within a tank and accumulate and be found in the lower parts of a tank. > 1As1 «Vapor Condhlone of Poeun gts4.4.1.4. Vapor Conditions of Petroleum Liquids j ee From the figure it can be seen that the lower end products need not be considered as they tend not TI yield sufficient flammable gas concentrations al normal atmospheric temperatures (unlet |! rw Contaminated by low flashpoint materials). Kerosine and white spirits can yield sufficient gt concentrations at tropical temperatures, whereas gasolines will be over-rich in these temperatures, de will yield flammable mixtures in temperate climates. Crude oils and Motor and aviation gasolines tend ratures. The term over-rich means that tt give aver rich mixtures at all normal ambient temper t equilibrium gas/air mixture lies above the upper flammable limit. 7 1.4.2 VOLATILE PETROLEUM [te From this we can divide the previously classified volatile petroleum into two further classes: mT Class A - Ca¥goes yielding over-rich equilibrium.gas mixtures at all normal ambier atmospheric temperatures, these include crude oils, spiked crudes, Mot Fas and aviation gasolines. 7 Class B - Cargoes yielding gas mixtures in the flammable range within the oa ambient atmospheric temperature range. These include kerosines a aviation turbine gasolinies and must include residual fuel oils as previa — mer pre 4.4.3 LOADED CARGO TANKS During the loaded voyage there Is usually time for equilibrium to be reached between the liquid rm and the gases in the ullage spaces above. In the case of Class A cargoes the mixture will be too rich support combustion. Therefore, ignition, explosion and combustion are unlikely. However, if a tank _ to be ruptured, the possible ingress of air could create a mixtdre within the flammable Alternatively, if gas is allowed to escape from the ullage space it would be diluted in the atmosphere and be capable of being ignited and burning, however any flame would be unlikely to travel back intof # = tank because of the over rich mixture inside the tank. It would be quite possible: for the flame continue to burn at the opening of the tank for a considerable period being fed by the rich gas inside the tank, and supplemented by further evaporation from the cargo inside the tank. 4 1.4.4 DISCHARGING CARGO TANKS During discharge, additional evaporation of the cargo takes place as the liquid level of the cargo i ee and the ullage space increases. However, because the movement of the air into the space Is e1 vy inwards there is little risk of the escape of gases to atmosphere and hence the risk of ‘external a and combustion is negated. With Class B cargoes if air is to be used to fill the vacuum which will be created inside the tank by outflowing oil then the likely result is for the gas/air mixture in the tank to be rapidly diluted below lower flammable level. This will significantly reduce the risk of ignition and combustion. aim atin Ta4.4.4.1 Formation of Vapor Layers when Discharging | Rapid dilution of the gas from Class A mixtures will also take place. The result of this is unpredictable ! nd it Is likely that the gas/air mixture within the tank will be within the flammable range for considerable periods during the discharge. The gas/air mixture within the tank will tend to layer into an over-rich layer immediately above the surface of the oll and a pure air layer at the top of the tank ullage space, In between these two will be a layer of mixed gas and air, which will contain some depth and will lie within the flammable range. The amount of mixing between the cargo gases and air, and the depth of layering ‘will depend upon the rate of discharge of the liquid from the tank and the turbulence created within the tank. Too Lean Flammable Vapour 7 SSS Volatile Oil being Discharged 1.4.4.1 - Formation of Vapor Layers When Discharging 145 EMPTY CARGO TANKS Alter the discharge of all the liquid cargo from a tank two processes continue. Firstly further evaporation of cargo vapours from remaining cargo residues within the tank takes place and secondly the gases will ©°, diffuse and disperse throughout the whole of the tank. Therefore, the tendency is for the gas xX sancentration in the tank to increase and become more evenly distributed. This may create an atmosphere within the tank too rich for combustion after Class A type cargoes. However, it is more ‘ely for the atmosphere to lie at some point within the flammable range. With Class B cargoes the likelinogd is for the atmosphere to remain too lean, but there will always be the possibility that some ‘may lie Within the lower end of the flammable range. > x1.4.6.1 Relationship Between Depth of Gas Layer & True Vapour Pressure Depth of Gas Layer - metres os ca a os er) uM 2 13 “ue ‘TRUE VAPOR PRESSURE - BAR Gas Layer Depth with 2 50% by Volume of Hydrocarbon Gas Relationship between Depth of Gas Layer & True Vapor Pressure146 TANK CLEANING The major operation during the ballast passage is tank cleaning. This will disturb remaining oil: ail jidues within the tank liberating more vapours and more thoroughly mixing the atmosphere , within the tank. This will increase gas concentrations within the tank creating a gas/air mixture within the flammable range or more likely over-rich after Class A cargoes, but increasing the risk of mixtures within the flammable range with Class 8 cargoes. As water washing continues in a tank the likelihood is for the gas/air mixture to dilute, which will mean that with class A cargo residues the mixture will move into the flammable range, 1.4.7 GAS FREEING ibsequenlly gas freeing he ta “te tammabie range, Further ie to this is made in Chapter 4, ‘Section 4.1.4.16, Continuing the’ preceding af dares, as already stated, it is assumed.that fresh air is directly introduced into the tank without aa ut the purging operation. Gas freeing aller washing is 2 debs period. Where fresh air is deliberately introduced into _jhe tank to ventilate and displace the hazardous gases from the tank(s). After Class A cargoes the too “Tich atmosphere will be diluted through the whole flammable range until all the gases have been displaced from the tank, With Class B cargoes if the atmosphere has entered the flammable range, it should be quickly diluted below the lower flammable limit and become too lean to support combustion. Gas freeing will also create hazards outside of the tank as the vapours leave the tank and are diluted with the outside air, into and through the flammable range. If washing has nol been thoroughly carried ‘out any remaining residues can liberate more gases after washing and gas freeing, this is particularly possible with crude oils, recreating possible dangerous atmospheres within the tank. 1.4.8 LOADING CARGO TANKS During loading, when cargo oil is first introduced into a tank, sapid evaporation from the liquid surface takes place. There is also considerable turbulence, which increases both the rate of evaporation and _the amount of mixing with the atmosphere within the tank. This will create a concentrated layer of rich gas immediately above the liquid. Above this layer will be a gas/air mixture which may lie within the flammable range. As the liquid level rises and the turbulence of the liquid surface reduces, the mixing of, gases is rapidly reduced and the original tank atmosphere above the small- mixing layer remains undisturbed, It is not until the latter stages of loading that the atmosphere being displaced from the tank * enters the flammable range as vented gases are mixed with the outside air. If the gas concentration | being vented from a tank was to be graphed this would show initially a gas concentration of almost zero ‘or well below the lower flammable limit. This would continue until the greater portion of the tank was loaded when the layer of gas/air mixture would begin to exit the tank At this stage, the gas ! concentration would slowly increase through the flammable range until the liquid level in the tank was ~close to maximum. There would then be a sharp rise in the gas concentration as the heavy layer of rich gas immediately above the liquid surface began to exit the tank. iplea eee ee See |e ae piel AEP gr ay iY ir oF ogy uF i 4.4.8.1 = Typleal Hydrocarbon Content of Vent Gas During Loading of Crude Oil Typical Hydrocarbon Content of Vent Gas During Loading of Crude Oil 1.4.8.448.2. Cargo Vapor Concentration, Half Tank Loading ‘Venting Air Air Too Lean Flammabie Too Rich Oil Cargo Loading 4.4.8.2 - Cargo Vapor Concentration, Half Tank Loading SEER HEE EEE ERE HEHEHE BH HE EY1.4.8.3 Cargo Vapor Concentration, Cargo Tank Nearly Full Venting Flammable Vapor Flammable Vapor Too Rich SSS Et} Cargo Oi 4.4.8.3 - Cargo Vapor Concentration, Cargo Tank Nearly Full erefore, it can be seen that during the loading process with Class A cargoes the atmosphere inside ¢ tank will contain some portion that lies within the flammable range and eventually become too rich ‘upport combustion, At the vent, the atmosphere will rise through the flammable range. With Class B s it is likely that the atmosphere will remain too weak to support combustion. § HIGH VAPOUR PRESSURE ally, it must be mentioned that with high vapour pressure cargoes when the cargo first enters the the gas evolution can be extreme with the cargo Iiterally boiling off. The vast amounts of gas being etated will quickly displace the atmosphere within the tank and at a great velocity. This quickly Nges the atmosphere being vented from the tank to almost pure hydrocarbon gas concentrations. Clearly presents a considerable hazard whilst loading these cargoes.— 4440 RESIDUAL FUEL OILS n Section 1.2.5, residual fuel oils are capable of producing flammable This is caused by the light end hydrocarbons in the fuel as previously mentioned ji oil is stored at a temperature well below its flash point < atmospheres within the ullage space of a tank. pourizing off. This can occur even when the spiemperature. «& This is especially relevant when residual fuel oils are being carried as a fuel where the tank would most ely not be protected by inert gas, In this case, the preceding arguments of loading, carrying and discharging tanks are most appropriate, Residual {uel oils must be treated as volatile and as such the precautionary measures as outlined in the ISGOTT book, Chapter 24 must be followed. Careful, frequent and regular monitoring of the tank ullage space is essential, in order to ascertain if a ted. If this Is the case, the space should be purged to reduce the flammable atmosphere is being generat vapour concentration and all precautions taken to avoid sources of ignition. Vent flame screens should be well-maintained and portable screens filed over sounding and ullage hatches when filing tanks. As these tanks are likely to be heated, excessive andlor localized heating must be avoided. When | tanks are ne: i _ Tammable vapours.” < IAI precautionary measures against static electrical discharge must be taken, when operations involving, ullaging, sounding and sampling are carried out. Electrical equipment must also meet appropriate 1 safely standards, 1.4.14 INERT GAS From the above discussion the benefits of replacing the tank atmosphere of fresh air with inert gas can be clearly seen. It is re-emphasized that inert gas must be used in all cargo handling operations. Inert Gas and its toxic hazards are further discussed in Section 1.11, Inert Gas System, its equipment © and use are discussed in later chapters. ¥ 44.42 COMBUSTIO! PI ION 4 NB ERPLOBION, gon an in summary from the preceding discussion on the nature of hydrocarbon oils, the hazards of flammability are easily seen and should be borne in mind when later sections are reviewed concerning the equipment and operations carried out. 4 ‘The process of burning fapidly expands the products of ‘combustion. When this | takes place within an enclosed space the pressure within the space increases until it bursts its confines and allows the excess pressure to escape - this is an explosion! With the rupture of a tank created by an explosion, relief of the pressure above the liquid will end to liberate further gases and with the rapid ingress of fresh air will create the right conditions for continued combustion of the vapour given off by jue liquid.