The formation of coal

Coal is a fossil fuel formed by the decomposition of land plant remains that have accumulated in swampy areas. Land plants first appeared in the Silurian Period 400 million years ago but it was not until the Carboniferous Period of 300 million years ago that these plants developed sufficiently to form the forests which produced the major coal deposits of the Northern Hemisphere. In Australia, which was then part of a great land mass called Gondwana (picture, right), coal formation occurred much later, in the Permian Period, 250 million years ago. This applies to the large deposits in Queensland and New South Wales. In Victoria, the coals are much younger; being deposited 15 to 50 million years ago during the Tertiary Period. In these waterlogged environments, plants and tree debris accumulated. As the layer of debris increased in thickness, the floors of these vast swamps subsided slowly and fungi and bacteria decomposed the plant material. This is the first stage in the "coalification" process and is characterised by extensive biochemical reactions. During degradation of dead plant material, proteins, starches and cellulose undergo more rapid decomposition than the woody material (lignin) and the waxy parts of the plants (the leaf cuticles and the spore and pollen walls). Thus the remains of many types of vegetation, including tree stumps, leaves, spores, seedpods, and resin are found in Victoria's brown coal. Some of the material is similar to existing vegetation but, in general, most of the plants have not grown in Victoria for millions of years. To varying degrees, and depending upon climatic conditions, plant constituents are decomposed under aerobic conditions to carbon dioxide, water and ammonia. This process is called "humification" and results in the formation of peat. This peat becomes covered with layers of sediment, which excludes air, and hence the second stage of coalification occurs under anaerobic conditions. In this second stage of the process the combined effects of time, temperature and pressure convert the peat firstly into brown coal (lignite) and then into sub-bituminous coal, bituminous coal and finally to anthracite. These three latter coals are usually called black coals.

would be formed. This transition from peat to anthracite is characterised by a number of chemical changes: 1.) 3. It includes hydrocarbons. The LaTrobe Valley coals show little variation in rank but do show considerable variation due to coal type (lithotype). Peat 7580 5060 5-6 3540 6065 Brown Coal 50-70 Sub-bituminous Coal 25-30 Bituminous Coal 5-10 Anthracite % H20 2-5 %C | Dry Basis | %H %O % Volatile Matter Specific Energy kJg-1 1 Dry Basis 2 Net Wet Basis 60-75 5-6 20-30 45-55 75-80 5-6 15-20 40-45 80-90 4-5 10-15 20-40 90-95 2-3 2-3 5-7 25 5 25-30 5-15 28-32 20-27 30-35 24-33 35-38 35-38 The chemical and physical properties of a particular coal are a result of the degree to which the above changes have occurred and exhibit considerable variation and rank. (This is the material removed when the coal is heated at a temperature >700°C in an inert atmosphere. Increasing proportion of carbon and greater proportion of carbon atoms bonded into benzene ring structure (aromatic carbon).The coalification sequence From this coalification sequence comes the concept of coal "rank" which is the measure of the degree of coalification or maturation. 2. At higher temperatures and pressures. The disappearance of cellulose. carbon dioxide and carbon monoxide. brown coal. 4. bituminous coal and eventually anthracite would be formed. Decreasing proportions of hydrogen and oxygen. given sufficient time. . Under mildest conditions the lowest rank coal. Decreasing proportion of volatile matter.

These fire holes can occasionally be seen on the exposed faces of open cuts. in the depth and nature of the swamp water and in the conditions of decomposition of plant material during this period result in the formation of coals with different characteristics. Variations in the botanical community. It is thought that in earlier times lightning caused exposed coal seams to catch fire and burn out holes in the coal. the largest found to date being roughly 250 metres across and 70 metres deep. Complete animal skeletons. In the first stage of coal formation (humification) organic acids are formed and it is the resulting acidic nature of the coal that leads to the decomposition of animal remains. however. no animal remains are found. animals drinking there sometimes drowned and were eventually covered when the holes filled with clay.It is estimated that the formation of one metre thickness of coal may have taken from 1000 to 4500 years to occur. . well preserved plant fossils are found in the coal. have been found in "fire holes" in the coal. Thus a seam 200 metres thick could have taken up to one million years to accumulate and form. These lithotypes can often be seen as distinct bands of different colour and texture on exposed faces of the LaTrobe Valley open cuts. as described earlier. It is worth noting that although. These holes filled with water.

nitrogen and organic sulphur with oxygen usually determined by difference. will influence boiler design.(%V. shrinkage and hardness. Physical Analysis Tests carried out in this analysis include surface area determination. Tests are typically done on samples taken from bores in the coal. Microscopic Analysis 1. the mineral matter in a coal will determine the ash formed and this. . = 100 .) which is expressed as a percentage of the dry coal mass and defined by: %F. It is important that the general composition of a particular coalfield is known. eg. in light of experience. in turn.). Chemical Analysis For practical purposes.Coal analysis There are three general types of coal analysis: 1. Chemical Analysis 2. Neither proximate nor ultimate analysis gives much information about coal structure but both give information that. The concentration of the macerals will indicate the coal type. + %ash) Ultimate or elemental analysis involves a quantitative determination of the percentage of carbon. 2. Microscopic Analysis This distinguishes the basic particles (macerals) in the coal. Physical Analysis 3. volatile matter content (V.M. Composition can vary significantly over a depth of a few metres. ash and. can be directly correlated with the behaviour of coal in most industrial processes. Specific energy determination determines the heat energy produced from the combustion of each gram of coal.M. 3. the chemical composition of coal is given in terms of its "proximate" analysis and by its "ultimate" or elemental composition. The above analyses are performed on brown coal.C. These bore samples are analysed at approximately three metre intervals. the fixed carbon content (F. as modifications to industrial equipment are quite specific for coal type. Proximate analysis determines moisture content. hydrogen. indirectly.C. mercury and helium density and porosity.

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CO. It burns according to the following equations: C + ½O2 => CO + heat CO + ½O2 => CO2 + heat The rate of this oxidation is controlled by the rate at which oxygen can diffuse onto the carbon surface. The levels of these oxides in the flue gases are low by world standards in the case of Victorian brown coal. these deposits are mainly composed of sulphates and silicates of Group I and II metal cations originally present in the coal. Burning of char residue. The ash formed from the inorganic components in LaTrobe Valley brown coal cause some problems in these large-scale operations: 1. therefore. In the case of Victorian brown coals. The char particle remaining after pyrolysis is mainly carbon and can be up to 50% of the dry weight of the original coal. an important component of any power . expensive technology to remove SO2 and SO3 must be incorporated into power station boilers. They are sometimes fused to the pipes and. hence.) A second problem can arise from water related corrosion. 2. The high porosity and surface area of brown coals and their chars. 2. CxHy . Individual coal particles pass through three steps in rapid sequence: 1. Components of the ash can cause corrosion of the water pipes. The latter two are burnt according to the equations: CxHy + (x + y/4)O2 => xCO2 + y/2 H2O + heat CO + ½O2 => CO2 + heat 3.The mechanism of coal combustion is complex. gives them high reactivity relative to higher rank coals. The oxides of sulphur and nitrogen produced in coal combustion can contribute to air quality problems.devolatilisation. H2O and hydrocarbons. although the final products are essentially CO2 and H2O with small amounts of sulphur and nitrogen oxides. This often involves "scrubbing" the flue gas with lime (CaO) slurry. Drying Pyrolysis . (It occurs on the fireside or outside of the pipes. chemicals dissolved in the water result in corrosion of the pipes from the inside. For example: (RCOO)2 Ca + ½O2=heat> CaO + 2CO2 CaO + SO2 + ½O2 => CaSO4 Where CaSO4 is left in the boiler or removed by the electrostatic precipitators. This will reduce the efficiency of the heat transfer o corroding the plant components. the ash is generally collected in electrostatic precipitators it can cause serious problems with the boiler by: o depositing on the outer surfaces of the water pipes. Hence. ie. This form of corrosion is called "fireside" corrosion. very difficult to remove. This step produces CO2. This is due to: • • the very small amounts of N and S in the coal the removal of some of these oxides by reaction with oxides of sodium and calcium formed in the combustion. In parts of the world where coals with much higher sulphur contents are used.

The structure of lowrank coal has not been widely investigated and. . Note with increasing coal rank: 1. Coals are highly porous solids with a large surface area. general structures can be proposed. Decreasing proportions of oxygen and hydrogen 2. its physical and chemical structures vary markedly with rank. hence. These model structures are consistent with the chemical changes that occur during coalification. except anthracite. Increasing proportion of carbon 3. The problem with these techniques is that it is often difficult to piece back together the fragmented products of the coal. A representative structure of a bituminous coal is given below. this porous structure is so extensive it makes the coal something like a solid sponge. but there is still controversy as to its proposed skeletal structure. Even in anthracite. often greater than 300m2 per gram for Victorian brown coals. To gain insight into coal structure. is poorly understood. attempts have been made to break the coal down into recognisable units and to piece them back together. attempts have been made to establish the molecular structure of coal.The Structure of Coal Like the composition of coal. Increasing aromatic nature These diagrams show representative partial structures for coals of different rank. For many years. are composed of units containing 1-3 condensed benzene rings linked by carbon chains containing various functioning groups. Currently it is believed that all coals. With the aid of modern spectroscopic techniques (x-ray diffraction and nuclear magnetic resonance spectroscopy) and knowledge of elemental analysis and the functional groups in coal.

Utilisation of Brown Coal The major problem in the utilisation of Victorian brown coal is its high moisture content. Unlike higher rank black coals. Combustion and electricity generation The most common method of upgrading Victorian brown coal is to burn it to generate electricity. For this purpose. Coarsely crushed new coal is fed to the boilers where it is finely milled (ground) in a combined milling/drying circuit. pulverised coal. recycled gases and evaporated water are mixed with preheated air and blown into the flame zone of the furnace where combustion occurs. This is because of the larger quantity of inert gas (water vapour and recycled combustion gases) which must be handled in the brown coal process. The boilers for electricity production from brown coal are much larger than black coal boilers of similar generating capacity. liquid or gaseous fuels of higher energy value. approximately 60 million tonnes per year are used to produce 85% of the State's electricity needs. brown coals have no export value in the raw state. The energy released is transferred to the boiler water by: • • radiation to the water tubes which line the walls of the furnace chamber. This high moisture content makes long distance transportation uneconomic and necessitates upgrading the coal close to the mine. This steam is used to drive the turbines that generate electricity. the coal is burnt in large-scale boilers. and convection from the hot gaseous combustion products (flue gas) which pass through banks of heat transfer tubes suspended above the furnace. This diagram illustrates the method of coal combustion currently used in the LaTrobe Valley. . which recover the heat of combustion as super heated steam. Ash particles are carried in the flue gas and electrostatic precipitators remove these before the flue gas is released into the atmosphere through the stack (chimney). The energy to dry the coal is provided by the hot gases recycled from the furnace chamber. The partly dried. This upgrading involves the production of electricity or solid. At present.

3. Cl.plant is the water demineralisation system. exchanges cations. In the sulphuric acid there is a high concentration of hydrogen ions and these displace the cations. In fresh resin. If we represent the anion as R. . cations in the water occupy these sites and the hydrogen ions wash through. The anions and cations of soluble salts are removed by ion exchange. Ion exchange The final stage in the purification process of river water to make it suitable for boiler use is the removal of the ions of soluble salts. known as an acid resin. which the resin has removed from the water.then the reaction can be represented by the following equation: Na+ (aq) + H+ R. known as basic resin. Ca2+. exchanges anions. the supply of hydrogen ions on the resin is reduced to the point that the resin is no longer effective. They are then large enough to settle out and be removed as sludge. One type of resin. Organic particles are removed by an ion exchange. The exchange is achieved by passing water through a tower containing small beads of synthetic organic resins known as ion exchange resins. having many centres of negative charge where cations can bond. In this case. Eventually. These hydroxyl ions are exchanged for anions in the water eg. the resin may be seen as a very large and complex cation. The principles involved are the same as described above for cation exchange. The colloidal particles are flocculated by the addition of aluminium hydroxide.. hydroxyl ions provide the balancing negative charge. these ions are hydrogen ions. The resin may be seen as a very large and complex anion. The resin is then regenerated by treatment with sulphuric acid. 2. When the impure water is passed through. at a power station such as Hazelwood) is carried out in four basic stages: 1. In fresh resin. This causes these very fine particles to clump together. The insoluble solids are removed by filtering the water through a vessel containing fine sand. The simplest resins are derived from styrene polymers. The exchanged hydrogen cations and hydroxyl anions then combine to form water. 4. such as Na+. This produces water in which the concentration of dissolved solids is measured in parts per billion! Water treatment plant The purification of the water used (up to 4 x 103 m3 per day. The anions are exchanged for hydroxyl ions and the cations are exchanged for hydrogen ions.(s) + H+ (aq) Another type of resin.(s) <=> Na+ R.

usually done in the presence of a catalyst Anaerobic Occurring in the absence of free oxygen Lithotype A variation within a particular coal rank. microlithotype or lithotypes Pyrolysis Destructive Distillation Carbonisation Decomposition by subjecting the coal to very high temperatures (600 . Lithotypes result from variations in the plants that formed the coal and the conditions of the formation Aromatic A structure including or based on the benzene ring Coalification A burial metamorphic process. including moisture Coal Rank The relative position of a coal in the coalification series peat to anthracite. Units are kJg-1 Gross Dry Results Analytical results that are expressed in terms of dried coal Volatile Matter This is removed when the coal is heated in an inert atmosphere (ie.Terms Of Reference Aerobic Occurring in the presence of free oxygen Hydrigenation The addition of hydrogen. in the absence of oxygen). The relative level of coalification determines coal rank Coal Type Determined by the plant and inorganic material which is deposited within a peat and the physical and biochemical conditions that prevail in the peat sedimentary environment. carbon dioxide and carbon monoxide and water formed by coal decomposition Humification The first stage in the "coalification" process. It results in the formation of peat . Coal type is best expressed in terms of macerals. involving physical and chemical changes that peat undergoes when subject to increasing temperatures and pressures consequent upon burial Macerals Particles within the coal which can be distinguished by an optical microscope Net Wet Results Analytical results that are expressed in terms of the coal as mined ie.1000°C) Specific Energy The heat energy evolved when a coal sample is burnt in oxygen. Often seen as a different coloured band in the coalface. It includes hydrocarbons.