2 Coal Deposits and Properties Coal Deposits Several terms are used by the U.S. Geological Survey to quantify coal deposits. "Total resources" are surmised to exist based on a broad interpretation of geological knowledge and theory. 1-4 Coals in thin as well as thick seams that occur in unmapped and unexplored areas to depths of 6,000 feet are included in total resources. "Identified resources" are those specific bodies of coal whose location, rank, quality, and quantity are known from geologic evidence supported by engineering measurements. Included are beds of bituminous coal and anthracite 14 inches or more thick and beds of subbituminous coal and lignite 30 inches or more thick that occur at depths to 6,000 feet and whose existence and quantity have been delineated within specified degrees of geologic assurance as measured, indicated, or inferred. Also included in this category are thinner and/or deeper beds that presently are being mined or for which there is evidence that they are commercially minable. Identified resources are about one-half of the total resources. The "demonstrated reserve base" (DRB) is a more restrictive classification and represents 100% of coal in place (measured and indicated) as of a certain date (see Table 2-1). DRB includes beds of bituminous coal and anthracite 28 inches or more thick and beds of subbituminous coal 60 inches or more thick that occur at depths to 1,000 feet, beds of lignite 60 inches or more thick that can be surface-mined, and thinner and/or deeper beds that presently are being mined or for which there is evidence that they could be mined commercially at this time. 13 10.7 -- -- -- - 127.7 - - - 366.1 17.5 4.4 697.5 10.7 17.5 21,141.9 39,984.9 6,501.6 13,098.2 6,077.2 12,693.5 67,705.0 4,541.5 10,621.1 2,198.6 4,482.0 1,644.0 994.8 411.0 289.0 14.0 25.5 96.4 25.7 67,705.0 424.3 3.73994.8 4.4 424.3 .7 8.1 1.1 255.3 366.1 997.7 997.7 826.2 127.7 826.2 Total-Bituminous Subbituminous 125.5 13,098.2 Anthracite 474,556.2 241,874.9 42,892.9 65,532.0 182,443.0 7,345.4 70,014.0 2,198.6 10,621.1 1,644.0 6,155.5 16,214.7 9,971.2 9,106.3 2,965.7 5,444.0 19,034.719,034.7 6,077.2 1,580.2 120,468.8 6,759.8 1,842.6 12,693.5 3,412.4 103,317.8 15,765.7 1,316.8 24,117.3 ,696.6 2.3 1,083.0 5,676.8 6,500.5 1,385.4 3,537.9 21,141.9 23,332.1 7,095.7 30,427.9 Coal Processing and Pollution Control 39,984.9 Lignite 14 ve Base*(million of Coalshort in thetons)1 United States on January 1, 1979, by Rank 9,971.2 Table 2-1 * Includes those parts of the measured and indicated resource categories as defined by the EIA and represents 100 percent of the coal in place. t Excludes coal-bearing states in which either the resources are not currently economically recoverable or the publicly available resource data do not provide the detail required for DRB delineation. ** Data may not add to totals shown due to rounding. tt Data shown not completely reconciled with DRB assessment by state. Coal Deposits and Properties -Principal deposits in Pennsylvania; and Virginia. Anthracite small - meta-anthracite Figure 2-1. Coal fields of the United States. Alaska.) deposits in Arkansas, Colorado. deposits in Massachusetts New 15 Me:o:ico. and Rhode Island (Coal rank not distinguished in The United States has major reserves of all ranks of coal: lignite, subbituminous, bituminous, and anthracite; their geographical occurrence is shown in Figure 2-1. Table 2-1 is a summary of demonstrated U. S. coal reserves classified by state and by grade.l The demonstrated reserve base (DRB) given in Table 2-1 is actually less than 10% of the total resources of coal that are believed to exist in the United States. The DRB does not include deep coals that could be recovered by evolving technologies, such as in situ gasification; this could expand the DRB significantly. 5 It is interesting to compare the U. S. total resources of coal with those deposits in other countries. Table 2-2 gives total resources as well as projected future production levels for major coal-producing countries in the world.3,4 Note that the reserve figure for the United States differs from that given in Table 2-1, due to the time of the estimate and different sources of data. It is clear that China, the USSR, and the United States all have dominant positions relative to coal resources, both inferred and recoverable. Data on properties of coals in different parts of the world have been presented by Singer. 6 Anthracite coal is the highest rank of coal, having the highest carbon content. Anthracite reserves are approximately 7 billion tons (all reference to tonnage is in "short" tons as opposed to metric tons) in the United States and are largely concentrated in the state of Pennsylvania. Bituminous coal, with reserves of 242 16 Coal Processing and Pollution Control Table 2-2 Coal Deposits and Production Reserves 49,560 183,866 27,533 61,356 1977-2000 108,902 4,672 15,419 113 1,982 730,102 22,026 4,625 ,434 Resources 47,357 13,686 65,639 37,906 121,035 4,295 3,6345,352,435 19,823 3,3042,830,403 209,252 36,123 11,839,029 1,583,753 660,795 355,767 252,384 3,414 7,379 271,807 153,910 89,228 79,295 * for the World in Million Tons of Coal* Production Cumulative Notes: I. Data is reported in million short tons (2000 Ib = I ton). 2. Data from World Coal Study and World Energy Conference.3 billion tons, constitutes the largest contributor to total U. S. coal reserves. Relatively high-grade bituminous deposits are found in the Appalachian regions of Kentucky, Ohio, Pennsylvania, and West Virginia. Significant bituminous coal deposits also occur in Colorado, and in the midwestern states of Indiana, Illinois, and Missouri. Bituminous deposits of lesser magnitude are located in the states of Alaska, Kansas, New Mexico, Utah, and Wyoming. Subbituminous coal deposits are of a lower rank than bituminous, but of a higher heating value than lignite. Significant quantities of subbituminous coal are found in the Rocky Mountain regions of Colorado, Montana, New Mexico, Utah, and Wyoming, usually in very thick seams, ranging over 100 feet in some cases. Total estimated U.S. subbituminous deposits are approximately 182 billion tons. Lignite is a low-rank coal. The two major deposits of lignite in the United States are in the Northern Great Plains and Gulf Coast regions, with limited deposits elsewhere. North Dakota and Montana contain large deposits of lignite. Other deposits occur in Texas and to a lesser extent in Arkansas, Louisiana, and Mississippi. Total tonnage is about 43 billion tons. The U.S. coal deposits can be classified by rank of coal, by method of mining, by heating value, and by sulfur content, as shown in Figure 2-2. More than twothirds of the total demonstrated coal reserves in the United States must be extracted by underground mining, because they occur at depths greater than 300 feet below the surface. 1.2 Most of the underground coal reserves are in the eastern and midwestern United States, while a major portion of the coal reserves that Coal Deposits and Properties 17 2% 9% By Rank By Method of Mining 3% By Sulfur Content Figure 2-2. Classification By Geographical Distribution of coal reserves. could be extracted by surface mining occur in the Great Plains or Rocky Mountain regions of the western United States. Figure 2-2 also indicates that more than half of the U.S. coal reserves are bituminous. Geographical distribution of coal deposits (Figure 2-2) indicates that approximately 17% of the total U.S. reserves are found in the Appalachian region and 25% in the interior region. Approximately 50% of the nation's total demonstrated coal reserves are found in the western region, which indicates the increasing importance of western coal reserves. The five most important factors affecting the selection of coal reserves for production are I. The transportation cost. 2. The heating value of the coal. 18 Coal Processing and Pollution Control 3. The depth of the coal deposits beneath the surface and nature of overburden. 4. Seam thickness and continuity. 5. The sulfur content of the fuel. The transportation cost is largely a matter of the distance and the mode selected; these issues are discussed in Chapter 4. The heating value determines energy content and is essentially a function of the rank of coal. The depth of coal deposits beneath the surface and nature of the overburden determine the mining method employed. Usually underground mining is used -with overburdens greater than 250 to 300 feet. Surface mining is used for shallower deposits. The seam thickness and continuity influence the specific mining practices as well as the resource recovery attainable for a given deposit. More details on extraction methods and their application to U.S. coal reserves are given in Chapter 3. Sulfur content is important in determining air pollution potential and ultimate environmental acceptability. It determines which desulfurization techniques can be employed in order to use coal in an environmentally acceptable way. In the early 1970s certain coals were classified as "low sulfur" coals, meaning that they could be burned in a boiler without flue gas desulfurization. However, the SOl standards have been tightened during the past ten years so that all coals now processed must be subjected to sulfur removal. The higher sulfur content coals tend to be found in certain Appalachian states such as West Virginia, Ohio, and western Kentucky plus the interior states of Illinois, Indiana and Missouri. Lowsulfur coal reserves tend to occur in some areas of the eastern United States (eastern Kentucky and southern West Virginia), but mainly in the western United States. The sulfur content of most U.S. coals ranges between 1% and 3%, giving an average of approximately 1.8% by weight. Coal Ownership Coal ownership is an important aspect of the utilization of coal reserves. A detailed estimate of coal ownership by type of company in the United States has been made by Schmidt. 4 This reference indicates the distribution of coal reserves with respect to ownership: public lands, oil (energy) companies, coal companies, and railroads. Total defined coal reserves by owner in the United States are approximately 300 billion tons as shown in Table 2-3. Of this total, approximately 187 billion tons are owned by the federal government, primarily in the western United States. Most of the federal coal ownership is in the states of Utah, Wyoming, Montana, Colorado, New Mexico, and Arizona. Significant federal action will be necessary in order to develop these coal deposits in the future. Coal Deposits and Properties 19 Table 2-3 Ownership of Coal Deposits by Industry in the United States4 Industry Classification Oil Companies Railroads Coal Companies Mining Companies Electric Utilities Steel Companies Other Groups Total Federal Government Number of Companies Coal Reserve 106 Tons 20 46,289 24,133 16,970 15,190 7,540 5,680 5,360 10 138 9 16 7 42 242 121,162 106 Tons Company 2.314 2,413 122 1,688 471 811 128 501 Percent of Total 38.2 19.9 14.0 12.5 6.2 4.7 4.5 100.0 186,855 The two largest industrial holders of coal reserves in the United States are not coal companies, but oil companies and railroads. A significant portion of the nation's proven coal reserves are owned by 20 different oil companies, for a total of 46 billion tons of coal. The average holding per oil company in this industrial segment is 2.3 billion tons per company.4 Consolidation Coal Co., a wholly owned subsidiary of Continental Oil Co., is the nation's largest single holder of coal, with reserves of 13.3 billion tons. Exxon is the second largest owner of coal from among the oil company group. Peabody Coal Company is the largest of the coal companies with a total reserve base of 9.0 billion tons. Burlington Northern Railroad owns almost half of the railroad-owned coal reserves with 11.4 billion tons, or 47.2 % of the total. An additional 41 % of the railroad coal is owned by the Rocky Mountain Energy Company, a wholly owned subsidiary of the Union Pacific Railroad Corporation, with a total coal holding of 10.0 billion tons. These two large western railroads control more than 24.4 billion tons of coal, or nearly 90% of the total coal holdings owned by railroads. Coal Properties Coal has its origin in fresh water swamps, analogous to the modern-day peat bog. Peat is a porous brown mass of organic matter (e.g., remains of roots, leaves, twigs, and trunks) in which the plant material is clearly recognizable.7 Peat accumulation requires conditions which have a low level of bacterial activity, slowing the rate of decomposition, namely I. Abundant flora. 2. Excess moisture or high water table. 3. Low temperature (70° -120°F). -----------------.--------- -.--===============~----------------_._---_._----- 20 Coal Processing and Pollution Control 4. Low concentrations of carbon, phosphorus, and nitrogen with partially oxidizing conditions. 5. Very high or very low pH (optimum pH for metabolic processes is 6.5 to 7.5). If the rate of decomposition of organic material is too rapid, peat will not accumulate. Peat accumulation usually occurs during periods of active tectonism or mountain building, leading to rapid burial of peat. The geologic periods exhibiting these characteristics-the Upper Carboniferous, Permian, Upper Cretaceous, and Tertiary-account for 94% of coal formed. Eastern U.S. coals were formed during the Carboniferous period (300 million years ago), while most reserves of western coals have their origin in the Tertiary period (60 million years ago), with the rest arising from the Cretaceous period (160 million years ago). The coalification process begins with the biochemical decay of dead organic material, which produces peat. This first stage of coalification, called diagenesis, involves attack by aerobic as well as anaerobic microorganisms of the plant material (cellulose, hemi-cellulose, lignin, fats, waxes, resins, and proteins). Microbial activity continues until the decaying mass becomes too acidic to support fungi and bacteria (growth ceases at pH of 2 to 3). Sulfur appears in coal due to the presence of sulfate ion; sulfate ion is reduced to sulfide by bacteria and combined with ferrous iron to form pyrites. Metamorphism is the second stage of coalification. Pressure and temperature along with time are the major factors controlling this step. Metamorphism is associated with a decrease in water content, loss of oxygen, and an enrichment of carbon, which also increases the calorific value of coal. Burial by succeeding layers of sediments subjects the peat to increased pressure, with heat provided by the natural geothermal gradient. A series of chemical reactions occurs during metamorphism, mainly stripping and condensation, where the oxygen and hydrogen contents are decreased due to heat addition. The condensation reactions eliminate functional groups such as -OH, -COOH, -OCH3, and -CH3 from the coal matrix. Peat will form lignite when exposed to slightly greater temperatures and pressures than found at the surface of the earth. If lignite, which is a very soft coallike material, is exposed to a greater depth of burial or a higher temperature, it may metamorphose into bituminous, or soft coal, and eventually into anthracite, or hard coal, and graphite. "Rank" represents the degree of progressive alteration that the organic matter has undergone from lignite to anthracite. Coal Petrography Coals can be classified according to the origin and nature of the plant material. NeaveF has called coal a "fruitcake" because of its diverse ingredients. Microscopic (petrographic) study of the visible features of coal is the basis of coal pe- Coal Deposits and Properties 21 Table 2-4 Coal Macerals and Maceral Groups9 Maceral Group Maceral Composed of or Derived from Vitrinite Collinite Tellinite Humic gels Wood, bark, and cortical tissue Liptinite/Exinite Sporinite Cutinite Resinite Spores Leaf cuticles Resin bodies and waxes Alginite Micrinite Macrinite Algal remains Unspecified detrital matter, < 10. fLm Similar, but 10-100 fLm grains Semifusinite Fusinite Sclerotinite Fungal sclerotia and mycelia Inertinite "Carbonized" woody tissue trography;7.8 polished coal specimens are examined mainly in reflected or transmitted light. Petrographic components are called macerals, which are to coal what minerals are to rocks. Macerals are divided into three groups: vitrinite, liptinite (exinite), and inertinite. These macerals are identified under a microscope by using incident light comprised of a plane-polarized beam that is monochromatized. Based on the refractive index and absorptive index at different locations on the specimen, a property called reflectance can be computed which determines the rank of the coal.7 Vitrinite is the commonly occurring maceral, arising from gels, wood, and bark. Vitrinite appears translucent by transmitted light and gray by reflected light. In reflected light, liptinite is dark gray and inertinite is white. Table 2-4 summarizes the coal maceral groups and their origins.9 The amounts of each group are found by heating the coal with an inert gas. Inertinite includes the inert infusible diluents in coal, while the first two components are subjected to chemical change. Liptinite is composed of bitumen, exinite, and resinite. A typical vitrinite fraction for U.S. coals is 70% to 80%, while inertinite is on the order of 10% to 15%. The exinite fraction is usually very low. Chemical Structure of Coal Structure at the atomic level of coal is difficult to investigate because coal is insoluble in common solvents and is generally non-crystalline and nearly opaque. These properties make analysis of structure via either spectroscopic or wet chemical methods very difficult. Coal has no repetitive structure, but rather is a mixture of macromolecules. Each seam and each sample is different in its composition, structure, and properties. The macromolecular entities in coal are probably composed of sub-units, some of which may themselves be released 22 Coal Processing and Pollution Control more or less intact upon mild dissolution or by other chemical treatments which only affect the weakest bonds. Several investigators have attempted to characterize coal in terms of a statistical average, including 1. Molecular size distribution. 2. Sizes and types of sub-units (including such features as their aromaticity and chemical functionalities). 3. Degree and types of crosslinking between sub-units. Coal is presently believed to be a highly cross-linked amorphous copolymer with weak links (usually aliphatic) between stable cluster units (average molecular weight of a cluster, composed of two to four fused rings, ranges from about 200 to 500). However, the actual structure varies with rank.7.10.11 Most of the hydrogen contained in coal is aliphatic, with relatively few methyl groups. The degree of carbon aromaticity ranges from 60% (lignite) to 80% (bituminous), depending on coal rank. The molecular weight of coal probably ranges in the low thousands. Oxygen is mainly contained in a phenolic (-OH) form, but also with some ethers, carboxyl, and carbonyl groups. Sulfur functionality is similar to oxygen, as thiols (-SH), ethers, or thiophenes. Nitrogen appears mainly as pyrrole and pyridines. Several molecular models have been proposed, notably the Given and Wiser models. 10,11The Wiser model for the coal molecule is depicted in Figure 2-3, Organic structural aspects of coal are very important in understanding coal liquefaction and pyrolysis behavior (see Chapters 6 and 8); however, coal structure is less important in coal gasification and combustion because of the severe chemical transformations involved in these latter two processes. Ultimate and Proximate Analyses It is customary to report the components of coal using two different analyses: "ultimate" and "proximate." The ultimate analysis from a dried sample is defined as the chemical determination of carbon, hydrogen, sulfur, nitrogen, and ash found via complete combustion of the coal; oxygen, the remaining component, is normally estimated by difference (although other methods to avoid indirect measurement are used on an experimental basis). Table 2-5 gives representative values for the ultimate analysis for a range of coal ranks,9 In addition, an elemental analysis of the ash can also be performed, and the heating value for coal is obtained using a bomb calorimeter (ASTM D 2015), Usually the higher heating value of coal (determined by assuming water in the combustion products is in the liquid state) is reported6,12 in the U.S. (Europe normally uses the lower heating value,) Coal Deposits and Properties 23 H I o H H H H-C-H -++ -.+ H-C-H H-C-H '- S 1 H H Figure 2-3. Wiser molecular model for coal. Table 2-5 Variation of Chemical Composition II 3 21 24 50 5 63Oxygen 71 74 35 Carbon 44 94 84 100 59 Hydrogen * Values are representative with Coal Rank9 Mass Percent" averages. dry basis. t Not a coal. The ultimate analysis can be used to predict an approximate heating value of the coal using the rule of Dulong and Petit, 12 which is HHV = 14,600C+62,OOO (H-O/8)+4,050 S -------------~_._._._._._._-----------_._---------------------------._------.--~--.-._-_. -,- __ 24 Coal Processing and Pollution Control where C, H, 0, S express the weight fraction of one pound of the major atomic components of coal. 12 In this equation oxygen is assumed to be combined with hydrogen as water, which is only an approximation. Other correlations found to be more accurate than the above equation for certain types of coals have been reviewed by Ergun 13 and Ringen et al. 14 Errors in measuring heating values can arise from the lack of a representative sample. The proximate analysis is defined as the determination of moisture, volatile matter, and ash, with fixed carbon determined by difference. The proximate analysis provides information to identify coal rank; while there have been several criteria proposed to determine rank,6 the accepted ASTM classification is based on the proximate analysis and the calorific values on a mineral-matter-free basis. Table 2-6 summarizes the ASTM D 388 classification of coals by rank and the calorific value ranges. The use of Table 2-6 does not, however, provide a satisfactory method of categorizing the physical and chemical behavior of a range of coals; NeaveF has argued for a different classification based on petrography. Table 2-6 shows that anthracite has a high percentage of fixed carbon and little volatile matter. It is thus hard and very brittle, dense, and shiny black. Bituminous coals form the largest group of coals in Table 2-6. They derive their name from the fact that when heated, they often are reduced to a cohesive, binding, sticky mass. Their higher volatile content makes bituminous coals more attractive for combustion. A distinct granular structure exists for bituminous coals, which are grayish-black in color, and some of these coals are soft and crumble easily. Subbituminous coals are brownish black or black, and generally have a high moisture content (15% to 30%). When these coals are dried, they tend to break apart. Lignites, the lowest coal rank, are usually brown and of a laminar structure due to woody fibers. Lignite is usually high in volatile matter and moisture content and disintegrates rapidly after losing moisture to air. Unconsolidated lignite is also known as "brown coaL" Brown coals are generally found close to the surface with more than 40% moisture. The proximate analysis serves as a simple means for evaluating coal characteristics. When the coal is heated, water vapor is first released at the boiling temperature of water; this weight loss is called the moisture content. The second loss occurs when coals are heated in a covered crucible, which prevents the oxidation of the carbon residue. This weight loss, called volatile matter, is measured as the coal is heated in 7 minutes to about 1750°F (950°C). If the remaining residue is subsequently combusted, the residue left after the combustion is called ash, and the weight loss on combustion is the fixed carbon. The proximate analysis of a coal is not a difficult operation, and is described in ASTM D 2013 and D 3175. Several commercial instruments automatically perform the proximate analysis. The following paragraphs discuss several aspects of the proximate analysis parameters. Calorific Fixed Carbon Class I. Anthracitic I. Subbituminous II. Bituminous III. Subbituminous IV. Lignite (Dry, MineralMatter-Free (Moist, Mineral-MatterFree Basis) Basis) Equal or Greater Than - coal Limits, Btullb Group -781492988669283122 22 31 14 I. Meta-anthracite 2. 3. Subbituminous Subbituminous coal coal B 2. 5. High CBCbituminous I. Lignite Lignitevolatile A Value Limits, % - Agglomerating Character Equal or Less Than Greater Than Less Than 98 92 86 78 69 Nonagglomerating coal A coal 13,000 10,500 8,300 6,300 9,500 11,500 6,300 00 C11 :J 14,000 ro w ~. "0 -0 roO N 0 Q. "0 !!!. 10,500 8,300 9,500 13,000 14,000 11,500 Commonly Nonagglomerating Agglomerating agglomerating 0 (3IJ) 3-en 26 Coal Processing and Pollution Control Moisture. Water in coal is held in cracks, crevices, and large pores; however, studies of water absorption isotherms and absorption swelling experiments revealed that part of the water did not seem to be behaving as free liquid water, but rather as chemisorbed and/or hydrated water. There is evidence that the rate of heating, the final temperature of heating, the period of heating at the final temperature, the composition of the surrounding atmosphere, the absolute pressure, and the particle size, all affect the amount of moisture driven away from a coal specimen. 13 The ASTM D 2013 procedure calculates three moisture values. First, if the coal is too wet to crush and sieve without losing moisture, it must be air dried (at 20°-30°F above room temperature), which results in the value of "air-dry moisture." The air-dried coal is then crushed and further dried in a forced-air-circulation-oven at 220°-230°F (l05°-11O°C) to constant weight. The weight lost in this step is referred to as the "residual moisture." The "total moisture" is the sum of the two weight losses. In the ASTM Standard Specifications for Classification of Coals by Rank (ASTM D 338), high volatile bituminous and lower rank coals are classified according to their calorific values on the "moist" basis. "Moist" refers to coal containing its natural moisture but not including visible water on the surface of the coal. As a means of estimating the bed moisture of coal, an equilibration method is used which is believed to restore the dried or wetted coal to essentially its bed moisture condition. The method consists of wetting the coal with water, draining off excess water, and equilibrating the sample at 86°F (30°C) in a vacuum desiccator containing a saturated solution of potassium sulfate that maintains a relative humidity of 96%. Equilibration requires 48-72 hours, depending on the rank of the .coal. The equilibrated sample can then be air dried to obtain its air-dry moisture content and further dried to calculate its residual and total moisture. Volatile matter. Volatile matter consists of hydrocarbons and other gases that are obtained by distillation and thermal decomposition of coal. The main constituents of volatile matter include hydrogen, oxygen, carbon monoxide, methane, water, and hydrocarbons, which may liquefy or solidify at room temperature. The composition of volatile matter varies greatly for different ranks of coal. As discussed above, volatile matter is used to establish the rank of coals. Because of the arbitrary nature of this test, care must be exercised in comparing the results of volatile analyses based on ASTM D 2013 with those obtained from tests run in other countries using different standards. Fixed carbon. The fixed carbon is the combustible residue left after driving off the volatile matter. It is not completely carbon, and it usually contains small amounts of hydrogen, oxygen, nitrogen, and sulfur. The fixed carbon in a proximate analysis is calculated by difference using the percentages of moisture, volatile matter, and ash. Ash. Ash is the noncombustible residue after complete combustion of the coal. The weight of ash is usually slightly less than that of the mineral matter originally present before burning. During the burning process, various chemical and Coal Deposits and Properties 27 physical changes in the ash take place. Because the conditions of oxidation determine the number and extent of such changes, variability can be expected in separate determinations of ash content even for the same coal sample unless standardized procedures are closely followed, particularly for coals with relatively large amounts of carbonates or pyrite. The term "inherent" or "fixed" ash content is used to designate that portion of the ash content that is structurally part of the coal after the coal is pulverized and mechanically cleaned prior to use. Recently there have been many improvements in instrumental analysis which have been successfully applied to coal. Much of this laboratory technology has arisen out of the need to assess potential pollutant emissions from coal utilization. Appendix A gives a review of these modern developments in analytical chemistry. Below we discuss in more detail those constituents in coal which influence pollutant emissions when coal is utilized. Table 2-7 lists ASTM tests which are employed for analyzing various physical and chemical properties of coal. Coal Mineral Matter/Ash Coal is primarily an organic substance with varying amounts of inorganic material. This is due to clay, carbonate, or other mineral matter which was carried into the peat swamps during the initial stages of coalification. The mineral matter is usually external to the organic material and not chemically combined with carbon or hydrogen, although in some low-rank coals alkali and alkali-earth elements (e.g., Ca, Mg, Na, Ba, Sr, and B) are often combined with carbon or hydrogen. After combustion of coal, the inorganic material is found mainly to be associated with the ash, which can comprise from 3% to 40% of the original coal volume. The major minerals and species which occur in coal mineral matter include pyrite, quartz, kaolinite, illite, siderite, calcite, and sphalerite. 13 Due to the difficulty of quantitative analysis of the ash minerals, ash analysis is usually determined by chemical analysis for most elements in the residue produced by combustion of a coal sample at 1350°F. The oxidation is performed at a slow rate and low enough temperature to prevent fusion of the ash. This means that "ash" and' 'mineral matter" are not the same material, physically or chemically (although they are related). An alternative to high temperature ashing is a low temperature procedure (400°F) which uses an oxygen plasma. The oxygen breaks down the organic matter without major decomposition of the inorganic mineral species (see Appendix A). Tremendous variability in ash composition is exhibited by U. S. coals, as seen in Table 2-8. 12 Table 2-8 also shows other properties related to ash fusibility, both for reducing and oxidizing atmospheres. ASTM D 1857 discusses the procedures for determining the reference temperatures mentioned in Table 2-8. This test is an observation of the temperatures at which triangular pyramids or cones prepared from coal ash pass through certain defined stages of fusion and flow when heated N ex> oo e!.. \J (3 () Table 2-7 ASTM Standards for Testing Coal *D1756 *D2361 *D 291 *D 440 *D 547 *D 1857 *D1412 *D2014 Cubic Foot Weight of Crushed Bituminous Drop Shatter Test for Coal Dustiness, Index of, of Coal and Coke Fusibility of Coal Ash Equilibrium Moisture of Coal at 96 to 97% Relative Humidity and 30°C Expansion or Contraction of Coal by the Sole-Heated Oven *D 720 D 409 Free-Swelling Index of Coal Grindability of Coal by the HardgroveMachine Method *D2015 Gross Calorific Value of Solid Fuel by the Adiabatic Bomb Calorimeter DI812 D2639 Carbon Dioxide in Coal Chlorine in Coal Plastic Properties of Coal by the Gieseler Plastometer Coal D 197 *D 271 D 492 *D2234 *D2013 *D 410 D 311 D 310 *D 431 *D1757 *D2492 *D 441 * Approved as American National Standard by the American National Standards Institute. CD (J) (J) :S. (Q Plastic Properties of Coal by the Automatic Gieseler Plastometer n> :J D. Sampling and Fineness Test of Powdered Coal Sampling and Analysis, Laboratory, of Coal and Coke Sampling Coals Classified Ash Content According to Sampling Mechanical, of Coal Samples, Coal, Preparing of Analysis Screen, Analysis of Coal Sieve Analysis of Crushed Bituminous Size of Anthracite Size of Coal, Designating its Screen Analysis Sulfur in Coal Ash Sulfur, Forms of, in Coal Tumbler Test for Coal from \J Q. ~ o· :J oo ::t Q. Coal on --0 --- 047.27 u; Utah Texas Illinois Ohio 2900 25.026.0 4.04.0 0.20.5 0.60.7 0.51.0 ]48.0 1.2 6.6 7.0 1.5 ]1.06.6 0.2 20.0 4.25 0.81 22,250 62,290 20.]] 29.28 1.60 3.53 10.87 12.8 1.25 37.64 22.81 0.36 0.78 4.17 17.36 47.52 1.02 20.13 5.75 1.77 ]7.87 4.0 .6 41.8 0.1 1.1 117.6 1.97 0.28 0.85 1.00 22.96 3.30 CD ]4.10 .5 30.0 60.0 0.5 4.0 0.6 + 1.6 1.5 ]2.3 0.7 97.5 80.80 95.74 95.20 84.3 6.4 98.44 98.8 No.6 No.92,220 Pocahontas No.3 02.5 ]3.6 .6 01.30 2,180High Volatile bituminous 2,220 2,240 2,450 2,450 2,210 2,140 2,225 2,180 2,150 2,250 2,370 2,320 2,240 2,175 2,160 2,130 2,060 2,120 2,190 2,265 1,990 2,030 2,000 2,300 1,975 2,070 roo 2,030 2,420 2,460 2,300 2,540 2,610 2,290 West Virginia 2,385 2,430 2,]90 West Virginia Pittsburgh Wyoming Lignite Bituminous en 0.. "0 ~ ~. "U 0~ SiOz Temperatures ........ of Some U.S. Coals and Lignite ················ Low Volatile . 12 2,620 Table 2-8 Sub2,480 2,670 2,450 2,605 ~ "0 I» CD N 0 30 Coal Processing and Pollution Control at a specific rate. As with other coal analytical methods, this method is empirical and several different methods are employed worldwide.6 Four stages of fusion temperature are reported in ASTM D 1857: 1. Initial, or the first rounding of the cone. 2. Softening, when the height has diminished until it is equal to the width at the base. 3. Hemispherical, when the height of the lump equals one-half the width of the base. 4. Fluid, when the mass is no higher than 1/16 inch. The ash fusion temperatures can be used as an approximate measure to indicate the magnitude of coal-ash-deposit buildup in combustion or gasification. Generally high fusion temperatures yield low slagging potential in dry ash removal systems, while low fusion temperatures are required for wet-bottom (slagging) systems. The application of ash fusion data to predict fouling behavior in combustion or gasification facilities is not completely quantitative. Often correlations involving the ash composition are used to explain coal ash properties; e.g., the base to acid ratio: Fez03 + CaO + MgO + NazO + KzO SiOz + Ab03 + TiOz Those components in the numerator are the basic oxides, which tend to lower the fusion temperature. The acid oxides in the denominator tend to raise the fusion temperature. Other correlating groups employed to evaluate coal-ash behavior, especially as pertains to deposition on both furnace walls and convection surfaces, include6 1. Iron/calcium ratio 2. Silica/alumina ratio 3. Iron/dolomite ratio 4. Dolomite percentage 5. Ferric iron percentage More details on ash fouling in coal combustion are presented in Chapter 9. Trace metals present in coal are associated either with the mineral matter or the organic fraction. 15,16 Typical mineral associations include the following: Trace Element Mineral As, Be, Cu, Sb B, Cd, Zn, Hg B, Cd, Mn, Se, Mo, V B, Cr, Mn, Cd, Mo, Se, W, Zn B, Cu, F, Hg, Sn Pyrite Sphalerite Calcite Quartz Clays Coal Deposits and Properties 31 Those trace metals shown to have high organic affinities include selenium, strontium, arsenic, cadmium, boron, and antimony. 15These elements tend to be concentrated in coals, whereas trace metals generally associated with mineral matter tend to occur in concentrations not significantly different from their average crustal abundance. Table 2-9 gives some representative data for trace metal occurrence in U.S. coals;15 because of the wide variations in trace metal composition that may occur in U.S. coals, only the order of magnitude values are important in this table. Analytical procedures for trace element and mineral analysis are discussed in Appendix A. Coal Sulfur The total amount of sulfur in coal varies from 0.2 to 10 wt% but in most samples is in the range of I to 4 wt%. Two forms of sulfur occur in coal: organic sulfur, which is bound to the hydrocarbon structure of the coal and inorganic sulfur, which is the remainder. The typical weight fraction of these two general classes of sulfur varies from 40% to 80% inorganic sulfur. 2 Inorganic sulfur appears mainly in two forms: as pyritic sulfur (i.e., sulfur combined with iron as pyrite or marcasite, crystalline forms of FeS2) and as sulfatic sulfur in the form of iron, calcium, and barium sulfates. Exposure of coal to air can increase the amount of sulfatic sulfur via oxidation of the pyritic sulfur to sulfates. Variations in coal sulfur content are usually due to the mineral matter, which may vary widely in the same coal seam. The sulfatic sulfur is usually water-soluble and easily removed by washing (see Chapter 5). Organic sulfur is usually distributed in a uniform manner in the coal matrix including such functional groups as sulfidic (R-S-R'), disulfidic (R-S-S-R'), mercaptanic (R-S-H), and thiophenic (ringed sulfur compounds). No organic sulfur compounds can be isolated from coal without changing its organostructure, which is why organic sulfur is the most difficult form of sulfur to remove from coal. Analytical procedures for sulfur analysis are discussed in ASTM D 2492 as well as in Appendix A. Other Physical Properties Physical properties in coal vary systematically (although not always monotonically) with coal rank, so that many of them can be predicted from the carbon or volatile content of coal. Properties such as porosity, density, and surface area, pass through a more or less well-defined maximum or minimum, usually between ~85% and 89% carbon, and thereby reflect the rank-dependent surfaceto-volume ratio of coal, or the transition from bituminous to anthracitic coals. 17,18Some of the important properties are discussed in the following paragraphs. en c. 0N S' (") I!) 0 0Q.~ elements Antimony (Sb) ~ 0 -0- - Q. :3 ""U0.10 2.3 (Q 0.05 ""U <0.6 !:!!. 2.0 0.32 4.9 2.6 1.0 0.36 50 0.18 1.6 0.006 0.08 0.7 .0 630.7 300 0.70 0.7 2.0 0.75 231.2 1.7 .8 2.7 2.6 0.88 0.04 0.24 0.16 <0.75.5 1.4 0.007 <0.8 3.2 1.6 0.12 1.19 0.18 0.31 0.68 1.70 0.54 0.78 1.0 0.33 100 70 75 50 0.06 0.10 0.21 0.04 0.06 0.20 0.01 0.21 0.01 0.52 0.015 2.0 0.005 10.02 0.01 2.2 1.1 0.05 0.12 0.05 0.08 1.4 15 25 5.0 150 300 500 100 2.0 2.0 bituminous Bituminous o' Average Average Lignite (ppm) - 0.00 60.002 0.8 0.48 2.7 0.02 2.0 0.35 0.07 10 0.05 0.24 0.44 0.9 0.15 100 1.5 Anthracite - Worldwide Table 2-9 (,) Estimated en (1) pUKe.) ~ -u0- 0.46 0() en '0 5.5 2.7 1.0 0.18 0.012 II 22 6.1 1.3 0.2 1110 .0 1.6 30.45 0.60 15 1.5 220 5715 323 207 0.71 74 70.4 0.17 16 19 15 20 37 1000 63 0.12 14 25 10 25 90.30 0.21 0.25 0.13 0.7 10 1.20 1.6 44.7 720 77 0.20 15 37 0.34 IS 1.l0 2.2 12.3 11.5 7.7 1.3 0.16 0.6 1.4 0.11 0.06 0.3 2065 0.08 19 0.05 0.07 10 3.2 bituminous Bituminous en Average Table 2-9 Continued Average Lignite :J (D' '0 0c,,) ~. c,,) n> ~ - - 255 50 0.40 0.61 0.13 0.47 0.3 20 27 61 10 0.15 72 33 Anthracite - Worldwide 0.09 7.5 0.75 0.13 CD <3 Estimated mated a. 0~ en (1) .". ::3 (Q () () -u - -4.6 a0.1 5.3 0.50 0.17 2.3 0.07 6.1 2.2 1.7 0 S' 1010 10 20 I3100 3950 20 19 0.0 53 30 0.42 0.1 0.07 2.5 1.9 0.20 1.6 0.27 0.26 0.12 2.7 0.3 \.3 1.2 lOa I2.7 4.1 330 100 0.5 25 lOa 15 \.3 0.5 5.3 300 500 50.07 52.2 31.6 1bituminous .5 0.1 2025 2.90 1.6 \.3 30 2.5 13.3 1.9 0.50 Bituminous 0.98 Average Lignite ~ ~Average ::3 ::3 c)" Q. en -I - 5.4 lOa 20 50 16 53.5 1.5 0.1 10 Anthracite tI> - Worldwide Co) 0 Coal Deposits and Properties 35 Plastic properties. Plastic and agglutinating properties of coal are important in evaluating coking and combustion suitability. Certain coals (mainly bituminous) pass through a transient plastic state when the coal is heated. The coal successively softens, swells, and finally resolidifies. These coals are said to be caking (non-swelling coals are non-caking). There is no sharp dividing line between these two types of coals and there are wide ranges in plastic behavior. The freeswelling test, as outlined in the ASTM procedure (D 720, entails heating of 1 gram of - 60-mesh coal in a silica crucible to 820°C (± 2°C) in 21/2 minutes, and determining the free-swelling index (FSI) by comparing the resultant "button" with a series of standard profiles. A noncoherent residue is assigned an index of 0, and indices of 2 or 3 usually imply that the coal is only marginally (or weakly) caking. An alternative method, which is used in some European countries and assesses the mechanical strength rather than the distension of a coke button, is the Roga test. 6 The ASTM has developed another semiquantitative procedure for determining the relative plastic behavior of coal when heated under prescribed conditions in the absence of air. ASTM D-1812 entitled, "Standard Method of Test for Plastic Properties of Coal by the Gieseler Plastometer," determines 1. 2. 3. 4. Initial softening temperature Maximum fluid temperature Solidification temperature Maximum fluidity A thorough discussion of the plastic properties of coal has been presented by Habermehl, et al. 19 and Berkowitz. 18 Porosity. Porosity in coal is composed of micropores «20A), mesopores (20A to 200A), and macropores (>200A). The micropores contribute mainly to internal surface area, while the macropores allow access to the inner pore spaces. Typical porosity is 25% to 30% for low-rank coals, 5% to 10% for anthracite, but only 1% to 2% for some bituminous coals, with the minimum porosity at about 91 % carbon (dry, ash-free, or daf). 17 Porosity is measured by mercury penetration under pressure. Surface area. The surface area of coal is measured by adsorption of either carbon dioxide or nitrogen. However, the measured area depends upon the specific adsorbate used, due to polarity and molecular size. Surface areas range from 100-200 m2/g (low rank), 50-100 m2/g (bituminous), and> 100 m2/g (anthracite). Note that the minimum surface area occurs with bituminous coal and not anthracite, at a daf carbon content of about 85% to 90%. Density. The bulk density of coal depends upon the degree of packing in the coal matrix. Usually this property is measured by helium or mercury displacement. Generally the density decreases as the coal rank is decreased, mainly due to the increased moisture fraction. High-rank coals can have densities over 1.5 g/ cm3, with 1.3 g/cm3 typical for lower rank coals. 36 Coal Processing and Pollution Control Hardness. The hardness or grindability of coal affects the relative ease of pulverization, as determined by ASTM D 409. More details on this test are given in Chapter 5. There are also several tests used to determine friability. 13 Reactivity. Coal reactivity may be defined as the rate that it combines with oxygen at temperatures above the ignition point; reactivity and rate of combustion are essentially synonymous. Reactivity generally increases as the coal rank decreases. Differences in reactivity from one coal rank to another can usually be explained by the changing levels in organically-bound oxygen with rank. Organically-bound oxygen is an inherent part of the coal structure, exclusive of water and mineral matter. As rank decreases from low-volatile bituminous to lignite, "organic oxygen increases by a factor of 5 to 6. When the fuel is heated, a portion of this oxygen becomes available for the oxidation process. Coal Sampling There are several procedures for sampling coal for various analytical tests. (See References 6, 12, 20, and 21.) Two sampling procedures are recognized in the present ASTM standard (D 492). They are the commercial-sampling procedure and the special-purpose sampling procedure. The "commercial-sampling procedure" applies to the average commercial sampling of coal. This procedure is designed to measure the average ash content of a large number of samples within ± 10% to a 95% probability. The "special-purpose-sampling procedure" applies to the sampling of coal when special accuracy is required. This procedure should be used to supply samples for the classification of coals and the establishment of design or performance parameters. The special-purpose sample can be one of two sizes, either 4 times that of the commercial sample, giving an accuracy of ± 5% of the ash content of the coal samples, or 9 times that of the commercial sample, giving an accuracy of ±3.33% of the ash content of the coal sampled.20 References I. Demonstrated Reserve Base of Coal in the United States on January 1, 1979, U.S. Department of Energy, DOE/EIA-0280 (79), Washington, D.C., (May 1981). 2. Averitt, P., "Coal Resources," Chemistry of Coal Utilization, M. A. Elliott, (Ed.), Wiley, New York, (1981), Ch. 2. 3. Wilson, C. L., Coal-Bridge to the Future: Report of the World Coal Study, Ballinger Publishing Company, Cambridge, Massachusetts, (1980). 4. Schmidt, R. A., Coal in America: An Encyclopedia of Reserves, Production and Use, McGraw-Hill Book Company, New York, (1979). Coal Deposits and Properties 37 5. Booz, Allen, and Hamilton, "Underground Coal Gasification Program," ERDA 77-51/4, Contract Ex-76-C-01-2343, (March, 1977). 6. Singer, J. G., (Ed.), Combustion-Fossil Power Systems, Combustion Engineering, Windsor, Connecticut, (1981). 7. Neavel, R. c., "Origin, Petrography, and Classification of Coal," Chemistry of Coal Utilization, M. A. Elliott, (Ed.), Wiley, New York, (1981), Ch. 3. 8. Bouska, v., Geochemistry of Coal, Vol. 1, Coal Science and Technology Series, Elsevier Scientific Publishing Company, Amsterdam, The Netherlands, (1981). 9. Probstein, R. F. and R. E. Hicks, Synthetic Fuels, McGraw-Hill, New York, (1982). 10. Whitehurst, D. D., "A Primer on the Chemistry and Constitution of Coal," Organic Chemistry of Coal, ACS Symposium Series No. 71, American Chemical Society, Washington, D.C., (1978), Ch. l. 11. Larsen, J. w., (Ed.), Organic Chemistry of Coal, ACS Symposium Series No. 71, American Chemical Society, Washington, D.C., (1978). 12. Steam: Its Generation and Use, 37th Edition, Babcock and Wilcox Company, Barberton, Ohio, (1972). 13. Ergun, S., "Coal Classification and Characteristics," Coal Conversion Technology, C. Y. Wen and E. S. Lee, (Eds.), Addison Wesley, Reading, Massachusetts, (1979), Ch. 1. 14. Ringen, S., J. Lanum, and F. P. Miknis, "Calculating Heating Values from Elemental Compositions of Fossil Fuels," Fuel, Vol. 58, No. 69, (1979). 15. National Research Council, "Trace Element Geochemistry of Coal Resource Development Related to Environmental Quality and Health," National Academy Press, Washington, D.C., (1980). 16. Torrey, S., (Ed.), Trace Contaminants from Coal, Noyes Data Corporation, Park Ridge, New Jersey, (1978). 17. Sharkey, A. G., and J. T. McCartney, "Physical Properties of Coal and its Products," Chemistry of Coal Utilization, M. A. Elliott, (Ed.), Wiley, New York, (1981), Ch. 4. 18. Berkowitz, N., Introduction to Coal Technology, Academic Press, New York, (1979). 19. Habermehl, D., F. Orywal, and H. Beyer, "Plastic Properties of Coal," Chemistry of Coal Utilization, M. A. Elliott, (Ed.), Wiley, New York, (1981), Ch. 6. 20. Gould, G., and J. Visman, "Coal Sampling and Analysis," Coal Handbook, R. A. Meyers, (Ed.), Marcel Dekker, New York, (1981), Ch. 2. 21. Swanson, V. E., and C. Huffman, Jr., "Guidelines for Sample Collecting and Analytical Methods Used in the U.S. Geological Survey for Determining Chemical Composition of Coal," U.S. Geol. Survey Circular 735, (1976).