Contents

Preface ................................................ Summary ............................................. Introduction .......................................... Origin of Methane in Coal..................... Methane Concentrations in Ship Holds Precautionary Measures ....................... At All Times ........................................... During Loading ................................... During Transit ...................................... During Unloading ................................ Spontaneous Combustion of Coal........... Early Detection of Spontaneous Combustion ................... Precautionary Measures ....................... During Loading ................................... During Transit ...................................... Glossary of Terms.................................. Figure 1................................................. Figure 2 ................................................

These Guidelines are intended to provide some general suggestions for the safe transportation of coal in dry cargo holds. They are not intended to supplant IMO Guidelines for Solid Bulk Cargoes for Coal Carriage or U.S. Coast Guard regulations. They should not be read as an all-inclusive statement of sufficient precautions for any set of circumstances. Because of differences in the characteristics of various coals and in their reactions to conditions preceding and during shipment, each situation is unique and requires that sound judgment be exercised beyond the general advice found herein. For that reason, the reader must be cautioned that, even if these suggestions are followed rigidly, methane emissions and/or spontaneous combustion could still occur.

Summary
The U.S. coal industry has transported coal overseas for nearly a century with few safety problems. Coal has not been classified as a hazardous material per se, but all carbonaceous materials, including coal, can contain some residual methane, and all are liable to spontaneous combustion if improperly handled. Therefore, it is necessary to take certain precautions with all types of coal to minimize hazards on ships. The propensity for spontaneous combustion is minimized if coal is loaded at near-ambient temperatures into clean, dry cargo holds with no air circulation. Fire or explosion due to the presence of methane cannot occur in the absence of an ignition source. Therefore, no open flames, heat source, or materials susceptible to sparking (such as aluminum) should be permitted in the vicinity of the cargo holds. All electrical installations in or near the holds should be explosion proof. Additionally, the void space on top of the cargo should always be ventilated prior to opening the hold covers.

These guidelines are intended to acquaint readers with some general precautionary measures necessary for carrying coal safely on ocean-going vessels. They describe the origin of methane in coal and how methane can create a hazard if adequate precautions are not taken the tendency of various coals to spontaneously combust is also discussed. Methods of early detection of spontaneous combustion, as well as precautionary measures necessary to prevent explosions and fires, are described. By following these simple guidelines, coal may be transported safely on vessels anywhere in the world.

certain circumstances, all carbonaceous materials, including coal, have the potential for spontaneous combustion. Problems usually arise only if coal is kept in a loose (un-compacted) aggregate and is exposed to air and/or moisture for an extended period of time. Uninterrupted growth of spontaneous combustion can ultimately lead to fire. These guidelines review this subject and list some of the necessary precautionary measures to detect and help prevent the spontaneous combustion of coal

Origin of Methane in Coal

Coal is a carbonaceous material formed by the bio-chemical decay of plant materials over millions of years. As a by-product of the coalifica-tion process, large volumes of gasses are formed, including carbon dioxide and methane. Methane is the most common hazardous gas found in coal mines. It is colorless, odorless, tasteless, nontoxic, highly flammable and lighter than air. The gas may be present in the cracks and fissures of the coal, but mostly it is adsorbed on the surface of the coal. Most of this gas is lost as the coal is mined, transported out of the mine and crushed and cleaned prior to shipment. Even after being loaded into rail cars or barges, coal continues to emit gas, although at an ever-decreasing rate. When coal is finally loaded into the ship holds, it has relatively little of its original gas left, but it still continues to emit some methane.

Introduction
Coal has been transported safely around the world for many years. The majority of this coal is transported overseas in ocean-going vessels without any safety problems. Improper handling of coal, however, can create dangerous situations. This booklet is written to acquaint readers with the potential dangers that may arise if coal is improperly handled. If proper precautions are taken, coal generally can be transported safely to all export markets. It is well-known that all carbonaceous geologic materials, including coal, contain some methane and will release much of this gas as they are mined. Coal continues to release methane, although at an ever decreasing rate, as it is processed, transported and shipped. If a hold in a ship is not fully loaded, the air in the empty space may mix with methane emitted by coal and form an explosive mixture. This gas must be vented prior to unloading the ship. Another potential danger is spontaneous combustion. Under

Methane Concentrations in Ship Holds

Methane, when mixed with air, can form an explosive mixture. The explosive range of methane in air is approximately 5% to 15% by volume. Above 15% the mixture is usually too fuel-rich to explode, and it is most often too lean below 5%. In either case, the gas-air mixture is non-explosive. Therefore, the concentration of methane must be kept well below 5% or well above 15%. At some higher concentration the mixture is not only non-explosive but is also non-flammable without the addition of more oxygen.1 The fuel-rich mixture can still become flammable in the presence of air and should still be treated very carefully. In most cases, keeping the concentration below 5% is preferred. However, there are cases where concentrations above 15% may be desirable. Methane-air mixtures can be ignited in many ways but most common ignition sources are pointsources of heat. Temperatures required for ignition are 650C to 750C (12021382F). Ignition sources include smoking materials, open flames, electrical arcs or sparks, sparks from rock or tool strikes, welding and cutting. The spark created by striking aluminum alloys against rusted steel 2 is especially dangerous. Silicon in the aluminum alloy also increases the sparking capacity. Aluminum smears or aluminum paint on rusted surfaces will also spark when struck with a hard object of any composition.

Precautionary Measures
Since all coals produce methane to some extent, some general precautions should be exercised during transport of coal.

At All Times
1. Smoking, any open flames or heat sources (such as welding or cutting) should never be permitted at or near the hatch covers of holds containing coal. 2. Chipping, scraping, or other potential spark producing activities should never be permitted in holds containing coal nor in adjacent areas. 3. Warning signs indicating "no smoking" and "no open flames" should be posted in all hold access points. 4. All electrical installations that are in the hold or near the hatch covers should be explosion-proof. 5. No aluminum materials, such as frequently found in paint, electrical conduit, tools or various containers, should be used in holds containing coal. 6. All vessels should carry on-board a portable device (or devices) capable of measuring 0 to 100 percent absolute concentration of methane gas and 0 to 100 percent of the lower explosive limit (LEL) of methane gas in atmosphere. Vessel personnel should be able to sample the atmosphere in the hold above the cargo without opening hatch covers or access panels. (See Figures 1 and 2 for suggested sampling arrangements.) 7. All vessels should carry portable, explosion proof exhaust ventilation fans (unless fixed ventilation systems are installed), self-contained breathing apparatus and should have personnel trained in the use of both.

During Loading
1. To the degree possible, each hold should be completely filled, thus reducing the amount of void space available for methane accumulations. 2. The coal should be evenly loaded and trimmed so as to prevent the formation of any void spaces that cannot be ventilated.

During Unloading
1. Prior to removing the hatch covers for unloading, methane measurements should be made to determine whether the air-methane mixture is explosive. Several measurements techniques could be used. The simplest and least expensive method would be the use of a portable methanometer. More accurate measurements could be made with other devices such as an infrared gas analyzer. If a gas monitoring system is in use, it will provide a continual measurement of methane concentration. Since methane rises in air, the measurements can usually be made in the top of the hold. Figure 1 shows possible locations to sample the atmosphere in the holds, and Figure 2 shows two types of sampling ports that can be installed. Sampling ports should be located at one end of a hold in as high a point as possible and as far from the nearest ventilator as possible. 2. The holds should always be ventilated before they are opened, regardless of the methane concentration measured. This may prevent an undetected pocket of methane from causing a fire or explosion. While the actual ventilation scheme will vary from ship to ship, the general approach would be similar in all ships. If there is an exhaust fan on the hold, it should be installed as far away as possible from the opening for air intake. (Blowing fans should not be used, because they could force air down into the coal itself.) This will permit the entire void space to be swept with fresh air. Once the void space is free of methane, as indicated by the methane measurements, the hold can be opened safely.

During Transit
1. During shipment, all ship holds containing coal should be checked daily for methane concentrations. A monitoring system can be installed on shipboard to check each hold. Continuous monitoring systems are commercially available at a moderate cost. Hand-held monitors are relatively inexpensive and can be very accurate. All instruments need to be kept calibrated at all times. 2. The master should make sure that all work spaces and passageways near and adjoining the hold do not have accumulations of methane. This can be done by routine, daily testing of the atmosphere. 3. If methane concentrations are found in working spaces or passageways, they should be ventilated immediately. No personnel, including those with self-contained breathing apparatus, should be allowed in such spaces until the methane content has been reduced to below 1% (20% of the Lower Explosive Limit). 4. The hatch covers and all entries to holds containing coal should remain closed for the duration of the voyage. 5. No personnel should enter a closed hold containing coal.

Spontaneous Combustion of Coal

Another hazard associated with handling and shipping of coal is spontaneous combustion. Spontaneous combustion (also called spontaneous heating or self-heating) refers to a rise in the temperature of coal without any outside source of heat. The actual process is a complex combination of chemical reactions. All coals exhibit some tendency toward self-heating under certain conditions. The primary reaction taking place during the early stages of spontaneous combustion is low-temperature oxidation. This reaction, taking place originally at ambient temperatures, consists of oxygen from the ambient air reacting with carbon (coal) to produce carbon monoxide, carbon dioxide and heat. If this heat is dissipated, the oxidation process will continue at a slow rate without significant danger of spontaneous combustion. However, if the heat is not dissipated, the temperature and oxidation rate will increase rapidly and the likelihood of spontaneous combustion will increase. It is generally believed that the rate of oxidation doubles for each 10C (18F) increase in temperature.3 The second reaction of importance is the process of moisture adsorption by coal. This occurs when the coal is dried below its inherent moisture content and then rewetted, either by water or through contact with humid air. This process provides extra thermal energy by a mechanism known as the heat of wetting, and it causes the temperature of the coal to rise.

Early Detection of Spontaneous Combustion

One of the best safeguards against spontaneous combustion is a means of early detection. Since the rate of temperature increase in coal is the best way to detect spontaneous combustion, reliable temperature measurements would best indicate the progress of spontaneous heating. However, since coal is a poor conductor of heat and the ship hold encompasses a large surface area, many temperature probes would be necessary to cover the entire hold, and the cost of temperature measurement could be prohibitive. The most practical early detection method for spontaneous combustion of coal in holds is a carbon monoxide monitoring system. Carbon monoxide monitoring has been used extensively to detect self-heating in underground coal mines for the last 50 years. Such systems rely on a steady increase in carbon monoxide with time to signal the early stages of self-heating. The carbon monoxide gas will diffuse throughout the hold containing coal, and a single monitoring point within the head space of each ship hold should normally be adequate. In fact, the same sampling location can serve for both methane and carbon monoxide monitoring as shown in Figures 1 and 2.

Precautionary Measures
During Loading The following precautions should be taken to minimize the occurrence of spontaneous combustion. 1. The first thing to avoid is loading coal that has already heated significantly in storage. Loading coal with bulk temperatures higher than 55C (131F) on the ship loading conveyor could promote oxidation and self-heating owing to the increase in oxidation rate. Coal undergoing heating during storage can be detected either by the presence of a coke-like odor or by use of an infrared camera. Terminal management should inform the master of any known heating problems prior to loading. If it is determined that the coal is indeed hot, it should be properly handled by terminal management to dissipate the heat prior to loading. 2. When loading, it is important that the ship holds are dry, free from standing water and free from foreign material such as cargo remaining from previous shipments. 3. The coal should not be loaded into holds which are in contact with any source of heat, such as steam pipes. 4. Size segregation of the coal in the hold should be avoided by spreading the coal across the entire hold instead of loading from one or two fixed positions. 5. The holds should be loaded as completely as possible to exclude air, trimming the surface to the walls of the holds.

During Transit Once the coal is properly loaded in the ship holds, the following precautions are necessary during transit to help prevent spontaneous combustion. 1. Exposing the coal to air and moisture should be avoided since both promote self-heating. It is recommended that the cargo holds remain closed. If methane ventilation of the holds is necessary it should be done over the shortest period required to reach desired concentrations. 2. In no case should water be applied directly to the coal. 3. Since toxic or flammable gases may be present, personnel should be prohibited from entering the holds. Such gases should be prevented from accumulating in adjacent, enclosed spaces. 4. In the event that entry is absolutely necessary, a selfcontained breathing apparatus should be worn at all times. The breathing apparatus should be worn only by personnel trained in its use.
5. Without question, the early detection

of heating is the best safeguard to help prevent the actual outbreak of spontaneous combustion. As discussed, temperature monitoring is expensive due to the large volumes of coal in the holds and insulating capacity of coal. For this reason, a carbon monoxide monitoring system may be more practical, and a monitoring procedure should be adopted on each ship carrying coal. The concentration could be monitored at least once a day on each hold as shown in Figures 1 and 2. If a sustained increase in the rate of carbon monoxide production is noted, sampling should be conducted more frequently, and the proper authorities

should be notified. If the carbon monoxide concentration continues to rise, the captain should attempt to decrease the rate of heating by checking the holds for points of air access and resealing. If heating continues, the captain should seek a port at which the affected coal can be removed. To provide for situations in which a port is out of range, it may be advisable for the ship to carry containers of an inert, heavier-than-air-gas (such as carbon dioxide) to arrest the spontaneous combustion and make the coal safe for carriage. This can be injected into the hold(s). APPENDIX Venting of a Hold Containing Gassy Coal During Transit Item 4 under the heading "During Transit" (page 4 of the "Guidelines for Ocean Going-Going Vessels Carrying Coal") is modified for those vessels that arc unable to have either a permanent or portable explosion-proof exhaust ventilation system for their holds.

4. Venting should be done, preferably, on a dry and clear day. Under no circumstances, should the coal be allowed to get wet.

Glossary
Ambient - The condition of the environment surrounding an item being considered; e.g. the ambient conditions at a coal stockpile are the outside temperature, barometric pressure, and precipitation level. Calorific Value - The heating value of a substance, often expressed as British Thermal Units (BTU) per pound or kilocalories/kilogram. Carbon Dioxide - A colorless, odorless gas formed during the combustion of coal; is nontoxic but can cause suffocation due to displacement of oxygen Carbon Monoxide - A colorless, odorless, toxic gas formed by the incomplete combustion of coal; reacts with blood hemoglobin to destroy the ability of the blood to carry oxygen. Heat of Wetting - The heat generated by the adsorption of moisture. Lower Explosive Limit (LEL) - The minimum concentration of methane in air that can cause an explosion, taken by most authorities to be 5%. Methane - An odorless, colorless flammable gas naturally released by coal that can produce an explosive mixture in air. Oxidation - The reaction of oxygen with another element or compound. Spontaneous Combustion - The self-ignition of a combustible material (such as coal) caused primarily by oxidation of the material. Thermal Conductivity - The ability of a material to transfer heat. 'Hertzberg, Martin; The theory of Flammability Limits; U.S. Bureau of Mines RI 8865, 1984, 36 pp.
2

"During transit," the hatch covers of holds containing very gassy coal can be opened temporarily for venting methane provided the following precautions are taken: 1. Prior to opening the hatch covers, all potential sources of ignition must be removed from the area. 2. Only non-sparking hammers and tools should be used to open hatch covers. 3. Venting should start when methane concentration in the hold reaches four percent and cease when methane concentration goes below one percent.

Desy, D.H., et.al.; Methane Ignition by Frictional Impact Between Aluminum Alloys and Rusted Steel; U.S. Bureau of Mines RI 8005, 1975, 30 pp.
3

Schmidt, L.O. and Elder, J.L.; Atmospheric Oxidation of Coal at Moderate Temperatures, Industrial and Engineering Chemistry, Vol. 32, No. 2, February, 1940.