CHAPTER 1 FUELS As an introduction to a study of fuels and their combustion, it is only proper that consideration be given to the amounts and types of fuels which are consumed in this country each year. It is interesting also to have some conception of the reserves of those natural resources known as fuels, so that a reasonable estimate may be made of the supply available for future generations. FUEL RESERVES AND USE OF ENERGY IN THE UNITED STATES ‘The fuel situation is a topic which has received a great deal of study from the U.S. Bureau of Mines, the various oil companies, private research organizations, and other interested parties. The extent of the national fuel reserves, because of the very nature of the problem, cannot be estimated with very great accuracy. Yet, it is desirable to have some knowledge of the available fuels and their relative costs. Figure 1-1 shows the quantities of energy consumed from the various mineral fuels and water power in the United States from 1889 through 1949. This includes energy used for all purposes such as the generation of electric power, and power for industry, the heating of homes, driving automobiles, trains, and airplanes. It can be observed that the use of energy has increased about fivefold since 1900 and has approximately doubled in the past 30 years. The estimated mineral fuel reserves of the United States are given in Table 1-1, This shows the actual reserve and rate of consumption as well as the equivalent reserve and rate of consumption in terms of 13,000 Btu per pound bituminous coal. ‘The last column shows an estimate of the probable number of years the supply of the mineral fuels now in use will be available, assuming that the rate of annual consumption remains constant. In summary, the table shows that the supply of coal will last approximately 1800 years, oil from petroleum about 12 years, and natural gas about 30 years. A graphical comparison of the yearly fuel consumption with the known reserves as of Jan. 1, 1948, is shown in Fig. 1-2. The reserves of coal have been established rather accurately for a num- ber of years and are probably fairly stable and reliable. On the other 12 FUELS AND COMBUSTION 40,000, O mat 1899 1904 1909 9S "BZD 1925 1530 1935 140 1945 1950 Fig. 1-1. Annual consumption of energy in the United States, 1899 to 1949, Energy from ‘water power computed at prevailing contral-station equivalent Btu per kilowatthour. ("Bituminous Coal and Lignite in 1949," U.S. Bureau of Mines, October, 1950.) Bituminous coal 37% Petroleum ‘Subbituminous 38% SOURCES OF 1949 PROPORTIONS OF ESTIMATED FUEL CONSUMPTION FUEL RESERVES, 1948 Fig. 1-2. Comparison of annual fuel consumption of various fucls with known fuel reserves in United States.FUELS 3 hand, the figures on the reserves of pétroleum and natural gas include only those oil fields which have been proved. New oil fields have been brought in more rapidly than petroleum has been used in the past. Con- sequently, while the use of petroleum has more than tripled during the past 30 years, the proved crude-oil reserves are greater now than in 1920. Tapue 1-1, Estimateo MINeRAL-FuEL Reserves oF THE Unrrep States, JAN, 1, 194s* Equivalent billions of net tons bituminous coal, | Reserve Reserve, esumedl 13,000 Btu/Ibt | divided Description Jan. 1, | ose | Coal, billions of net tone: | ‘Anthracite. | 7.5 | 0.060) 7.3| 0.6 | 0.06 | 162 Bituminous............| 700 | 0.600 | 728 | 55.6 | 0.62 | 895 Subbituminous. 409 | 0.014 | 299 | 22.8 | 0.01 Lignite........ =| 470 | 0.004 | 242 | 18.5 | 0.002 Total...... 1586.53 | 0.678 [1276 |" 97.5 | 0.69 | 1850 Petroleum, billions of bbl..| 24.7 | 2.0 5.7| 0.4 | 0.46 | 12.7 Oil from oil shale, billions OLD. ceeeeeeeesee.] 928 | 2.0 21.2/ 1.6 | 46) | 46.1 Natural gas, trillions of eu ft... seve) 165.9 | 5.6 6.4/ 0.5 | 0.22 | 29.1 Total, all fuels. 1309) 1.37 | 986 Carl E, Miller, The General Fuel Situation, Combustion, October, 1948, 1t Heating values used: Anthracite coal 12,900 Beu/tb 13,500 Biu/b 9800 Beu/lb 6,000,000 Beu/bbt te. 6,700 Btu/lb Natural gan 1,000 Beu/ou ft Data from Dr. A.C. Fieldne, Chief, Fuss and Explosives Branch, U.S. Bureaa of Mines, corested to Jan 1 1048 Figure 1-3 depicts the increase in proved reserves of petroleum as com- pared to the increased annual consumption. From this comparison, it is considered quite likely that the supply of oil from petroleum will be ade- quate for the next 20 to 25 years at least, and perhaps for a much longer period. Likewise, new gas fields are discovered each year, and it is con- ceivable that the natural-gas supply will be adequate for the next 50 years. Apparently it is reasonable to assume that a substantial supply of the solid, liquid, and gaseous fuels used today will exist for a good many4 FUELS AND COMBUSTION years, especially if synthetic liquid fuels from coal and oil shale are used to supplement the supply of petroleum. The use of foreign oil might also aid in conserving the petroleum reserves of this country. However, it has been estimated that the United States has about 35 per cent of the proved world reserve of crude oil, thus no substantial help from foreign fields is completely dependable, espe- cially in a time of world crisis when the drain on petroleum reserves is 4 2 ° erm MTOM 2 4 6 8 10] | 4 '6| 2a 26 1918 Billions of borrels 8 20 3a 32 Year Fig, 1-8. United States production of crude petroleum compared to proved reserves. ("Petroleum Data Book, 1947," and Mineral Industry Surveye, U.S. Bureau of Mines.) 3640 aa greatest. It is interesting to observe that the United States also enjoys the enviable position of possessing about 40 to 50 per cent of the world’s coal supply. Figure 1-4 shows the power output by different fuels from all private and public electric utilities from 1920 through 1950. It can be seen that water power is used to generate about 30 per cent of the power produced by electric utilities. However, the energy produced by hydroelectric stations represents less than 5 per cent of the total amount of energy used yearly for all purposes in the United States, as is shown in Fig. 1-1. ‘The principal users of bituminous coal and the relative amounts they consumed in 1950 appear in Table 1-2. In contrast to the diversified market for bituminous coal, anthracite is used for space heating almost entirely. ‘Table 1-3 shows the percentage yields of the major petroleum6 FUELS AND COMBUSTION shown recently in the development of synthetic liquid and gaseous fuels. With the coming of atomic energy, it is possible that within a few years much energy will be supplied from fissionable materials. Present devel- opments are reported to be along the lines of applying atomic power to KS LAT Electric utility generation by source of energy United States 1820—1950 vie Zh SESS ASS SSS 1920 22 24 26 28 1930 32 34 36 36 1940 42 44 46 49 1950 Fro. 1-4. Consumption of fuel for the production of electric energy. (Courtesy of Federal Power Commission.) the generation of electricity in large central stations and of providing motive power for marine vessels and guided missiles. Experts in the field are predicting that atomic piles will not be producing any appreciable quantity of central-station power soon. ‘Thus, barring an unforeseen revolutionary development in the atomic field, it seems that the present fuels and types of combustion equipmentFUELS 7 will be used for a good many years to supply the bulk of the heat and power needed in this modern civilization. SOLID FUELS The solid fuels used in this country primarily are bituminous and anthracite coal, coke, wood, and charcoal. Of these, the consumption of coal far exceeds the combined demand for the others, and most of the discussion here will be devoted to coal. Origin of Coal. Geological studies prove definitely that coal is of plant origin. During the initial period of coal formation, heavy vegetation in swamps and bogs built up a thick layer of partially decayed vegetal residue which was probably soon covered with water. Over a period of many centuries the decayed matter accumulated to a depth of several feet before it was buried by the violent earth upheavals, floods, and glaciers of the formative period of this planet. ‘Then began the secondary transformation period wherein the decayed vegetation was subjected to extreme temperatures and crushing pressures. It is believed this second stage must have lasted several hundred thousand years to transform the soggy swamp decay into the solid mineral known today as coal. In the course of the coalification, or coal-forming, process the moisture and gaseous inclusions in the original decayed vegetation were slowly excluded from the coal bed as a result of the pressures and high tempera~ tures exerted by the earth. ‘The extent to which coalification has pro- gressed determines the rank of a coal. The major ranks of coal from lowest to highest, are 1. Lignite 2. Subbituminous 3. Bituminous 4, Semianthracite 5. Anthracite There are no clear-cut dividing lines between coals of the various ranks, and different physical properties are sometimes listed to help classify fuels which are borderline cases between lignite and bituminous, or bituminous and anthracite. The method recommended by the American Society for Testing Materials (ASTM) and the American Society of Mechanical Engineers (ASME) to classify coals according to rank appears in Chap. 5. The accumulation of decayed vegetation first came to the stage where it'was known as peat. Peat is not a coal but represents the first stage in the formation of coal.. In the early stages of transformation, varying amounts of water, methane, and éarbon dioxide were gradually elimi-8 FUELS AND COMBUSTION nated. Further increases of pressure and temperature were then respon- sible for driving off much oxygen, volatile matter, and moisture as the peat was changed to lignite, and finally to bituminous coal. A few coal fields, principally in Pennsylvania, were evidently subjected to the coal- forming processes to a greater extent than most other areas, and in the coal seams there the volatile matter of the fuel was reduced still lower to form the anthracite coals, The composition changes which occurred during the coalification process are shown graphically in Fig. 1-5. 100 -" = 5 eo] 5 § 0 Lee z g SZ 20 <0 St ° Wood Peat Lignite Subbi- Bituminous Semi Anthracite tuminous ‘onthrocite: Fic. 18, Progressive changes during the coalification process. Percentages given aro on the moisture, ash, and sulfur-free basis. (Adapted from “The Making, Shaping, and Treating of Sied,"" Carnegie Steel Co, 1820.) Production of Coal. In the preceding sections, the extent of the coal reserves of the United States was discussed, but no mention was made of the areas in which these reserves were located. Figure 1-6 shows the states having the greatest coal reserves and also reveals the ranks of these fuels. For comparison with the location of reserves, Table 1-5 gives the production of coal by states in 1949. It should be noted the greatest coal-producing states are Pennsylvania, West Virginia, Kentucky, and Illinois, with Ohio and Indiana closely following, while the greatest reserves are in Wyoming, North Dakota, Montana, and Colorado. This lack of development of the western coal fields is due principally to the facts that (1) the demand for coal is greatest in the highly industrial East and (2) the rank of the eastern coals is considerably higher and the quality is more adaptable to present combustion equipment. Although most of the coal produced comes from underground mines, an increasing proportion is being mined yearly by strip mining. Table 1-5 also presents the extent of this type of mining in the various states in 1949. Coal veins in the United States vary from several inches to 40 ft in thick- ness, but the average coal seam is only about 4 ft thick. ‘The thickness of the vein and its depth below ground are two of the major economic factorsFUELS 9 W N Dakota Colorado Montana Wry hgjirio ivonia ‘Ohio Utah Missouri Aloborna Washington kichorna Indona ees [2 Anthracite Konsos Bituminous ors08 ZA Suidbiturinous Virginio [ZI Lignite Moryland New Mexico Others ° 30 10080200 880300 Billions of tons Fic. 1-6, Coal reserves by states, 1948, Tamue 1-5. Coat Provuction nx Srates, 1949* Rank of| Millions of met tons | torus State col | ana production | All mining | Strip mining Penaaylvania...........| Anthr. | 42.7 | Bitum. | 89.2 | ~ 131.9 | 27.4 West Virginia. Bitum. 122.6 25.5 | Bitum. 62.6 13.0 Bitum, 47.2 9.8 Bitum, 31.0 8.5 Bitum, 16.6 | 35 Bitum. 14.6 | 3.0 | Bitum. 12.9 27 | Bitum. 6.2 | 13 Bitum, 6.0 | 12 Bitum, 46 10 Bitum, 42 0.9 Bitum. 20.2 | 42 | 780.6 | 100.0 po “Mineral Industry Surveys, Bituminous Coal and Lignite in 1949, U.S. Bur. Mines, October, 1950,10 FUELS AND COMBUSTION which determine what type of mining will be most advantageous in » particular location. All mining has become more mechanized each year. As of 1949, 67 per cent of all coal mined underground was loaded mechanically, and 91 per cent was cut mechanically from the vein. Modern mining machines ‘such as the one shown in Fig. 1-7 are used extensively to cut the coal from the vein and load it automatically on rail cars in the mine. Such mining methods helped to increase the production per man-day, so that in 1949 the national average coal production was 6.43 tons per miner per day, the Fio. 1-7, The Colmol at work, ‘This modern machine mines and loads coal in one ope ion without the use of explosives. (Courtesy of Jeffrey Mfg. Co.) highest rate of production for any country in the world. This figure is still low as compared to the 15.33 tons per man-day produced by strip mining, which gives a comparison as to the relative ease of mining by stripping and other means. An increasing percentage of coal is being cleaned and sized at the mine. In the most modern mining operations, the coal is conveyed to a coal tipple at the mine entrance. Here the large lumps are crushed, and the entire production of coal is screened to yield products of a uniform size. Much of the coal is washed and cleaned to remove as much of the rock, sulfur, and other mineral content as possible. It is then loaded on ral cars or trucks for the consumer. Types of Coal. Coals may be classified as banded or nonbanded, according to the type of their petrographic, or rock, structure. BandedFUELS ay coal is not a homogeneous substance, but consists of alternate layers or bands of bright-black, dull-black, and gray metamorphosed vegetal material. Banded coals exist in all ranks of coal from lignite to anthra- cite. ‘The appearance of the bands is attributed to different kinds of wood and plant substances in various stages of decay. ‘The U.S. Bureau of Mines further classifies the banded coals as (1) bright, (2) semisplint, and (8) splint coals, depending upon the pre- dominant plant residues of which they are composed. Figure 1-8 shows a block of bright, banded, bituminous coal. ‘The extent and appearance of the bands are evident. The nonbanded coals are the cannel or bog- Fre, 1-8. A bright, banded, bituminous coal. (Courtesy of U.S. Bureau of Minea, Depart- ment of the Interior.) head types. Figure 1-9 is a picture of a lump of cannel coal. It is uni- form and compact in structure with little or no evidence of bands. Both cannel and boghead coals break ‘with sharp clean fractures as shown and are greasy black in appearance. They are high in volatile matter and produce high yields of tar and light oils upon distillation. Composition of Solid Fuels. Solid fuels are composed of carbon and hydrogen, with various amounts of oxygen, nitrogen, and mineral matter included. The chemical constituents of coals, coke, peat, etc., are determined by the prozimate analysis and the ultimate analysis, and typi analyses and heating values of various solid fuels are listed in Table 1-6. ‘These analyses are reported on the basis of the fuels as received at the laboratory and the heating values given are for both moist and dry fuels,12 FUELS AND COMBUSTION Ultimate Analysis. The ultimate analysis of a coal is a precise chemical determination in which the six basic components of the fuel—carbon, hydrogen, oxygen, nitrogen, sulfur, and ash—are listed in per cent by weight. The percentages of hydrogen and carbon are found by burning a 0.2-g sample in a strongly oxidizing atmosphere and weighing the quan- tities of carbon dioxide and water vapor emitted as the products of com- bustion of the sample. The carbon dioxide is absorbed in a solution of t ad Fra, 1-9, A cannel coal. (Courtesy of U.S. Bureau of Mines, Department of the Interior.) potassium hydroxide for weighing, while the water vapor is collected ina calcium chloride tube. The percentage of ash in the coal is found by heating a 1-g sample to approximately 1340 F. In the presence of oxygen, this high temperature assures the complete burning of all combustible in the fuel, and the residue is ash. The percentages of nitrogen and sulfur are found by complex chemical analyses on different small samples of the fuel. ‘The percentage of oxygen is computed as the difference between the sum of the percentages of the other five items and 100. Thus, the percentage of oxygen, as listed in the ultimate analysis, is subject to the accumulative errors of the other determinations. Proximate Analysis. The proximate analysis is a simpler test which shows a few important components of a coul sample without resorting to13 FUELS oe “| Lor|ee jos] ore | or | res | oat T0928) 3 ost} 90 | 60 | zit] sz | 999 | over | 8:99 | e+ | Oat "92034 240) = Lorjot jet (et |eo joes) cor rs} #1 | 80 gonpoxd-£q ‘2409 g gz jo | losrlos | ver! foe | Asp ‘oseuiug, . 961/90 |so jos | oe | $02 | o'er | 2-99 | oor] re 3A ‘aqperpusturag 26/40 |rr |ae joe |cos|i6 ees of | ¥q ‘oyousqaTEg 69 |s0 |so lez [az |zo8|eo jsus| re jee sg ‘TB00 ayIOETUY or | £0 | et | 9°6z]0°9 | 8:89) oF | 6'sF | g08 | 96 +0100) ‘sno Soe os je% jor |ret}es | g29| 98 | ree | sor | Var aa 2 os ar ler |rer|oe | Feo} 0% | eer | Toe | 38 osz‘FI | osz‘#I | oe | 9'0 | et joror} se | ze] ore | eee | ose | Te ous‘er | ose | ott | 20 [et | 1s |r | 692 | ort | r29| gee | Bz ogr‘yt | ogo'rr |e jor [st zs jos | ros) ez | 60] siz) re | ost'rt | ooz‘'er | os jor far |e jer |oez|os jeu | oor re oos'st | ore'st | 2-9 | st | tr [es or | 208] 29 | ovo | g02 | ee | ooo'rt jorz'z | 9 | 40 | 20 | eer] zo | rer] zo | soe | 2-82 | ere : ‘e |o9 | FO | eT | 96s) 96 | Tes] o-9 | err | o'92 | B99 go [fo | rorjos foes] . : vo vo | ge }o9 | e09 | swuq | popiod wot |uo8oxp| woq luogaeo| 9) aang faq | -a16y #0 | Ar | m9 | PY | pox | OF | -sroyy | “eA, pny qwvma ‘onqoa Sunyvoy % ‘shqouw ayeeaL % ‘wsdyous oyeunrxong PISA] GYIOg 40 BNOTLISOANOD TVOIUAL “9-1 GIHV14 FUBLS AND COMBUSTION the accurate chemical analysis required for the ultimate. It lists the four items: moisture, volatile matter, fixed carbon, and ash in per cent by weight. The percentage of moisture is found by heating a 1-g sample of the fuel to about 225 F to evaporate the water and by measuring the loss in weight of the original sample. By heating another 1-g sample in an airtight crucible for 7 min at about 1750 F, the volatile matter and the moisture are expelled from the sample without igniting the fixed carbon. The percentage of volatile matter is the loss in weight upon heating the sample minus the percentage of moisture already found. The percentage of ash is measured in the same manner as was explained for the ultimate analysis. Obviously, the same percentage of ash should be reported in the proximate as in the ultimate analysis. The remaining item, fixed carbon, is computed as 100 minus the percentages of moisture, volatile matter, and ash. ‘The heating value of the fuel and the percentage of sulfur are often given when reporting a proximate analysis of a coal in addition to the above four items which total 100 per cent. The heating value of the fuel is determined by burning a 1-g sample in a bob calorimeter with a large excess of oxygen to ensure complete combustion, as discussed in Chap. 3. From the heat emitted following the combustion process, the heating value, or calorific value, of the fuel can be computed. Under the condi- tions existing in the bomb calorimeter, the sulfur in the fuel burns and forms sulfuric acid upon uniting with the water vapor. The amount of ~ sulfur in the original fuel sample can be determined accurately by measur- ing the quantity of sulfuric acid washed out of the bomb calorimeter following the combustion process. If the percentage of sulfur were to be ineluded in the proximate, it would be accounted for twice, since it already has been reported, part being included in the volatile matter and part in the ash. ‘The moisture as determined for the proximate analysis consists only of the free moisture, or surface moisture, present with the solid fuel. Addi- tional hydrogen and oxygen may be contained in the fuel even after the free moisture is driven off, but they probably are not united to form water. The volatile matter consists of all gaseous products which can be expelled by heating the fuel. Fixed carbon is that carbon in the solid state which remains once the volatile matter and moisture have been removed. It does not represent all of the carbon in the coal, as listed in the ultimate analysis, because volatile matter contains considerable carbon in the form of complex hydrocarbon compounds. PETROLEUM FUELS Origin of Petroleum. Of the several theories advanced concerning the origin of petroleum, the theory of vegetal origin is the most widelyPUELS 15 accepted today. It holds that enormous quantities of gelatinous vegeta- tion accumulated in clays and sands along seacoasts or lakes. Shifting currents then buried the organic material in layers of sediment which pro- tected it from the normal processes of decay. Subsequent changes in the earth structure eventually subjected the entrapped vegetal matter to enormously high pressures and temperatures which brought about a type of semidestructive distillation. This along with other metamorphic proc- esses resulted in the formation of petroleum. Geologic studies indicate that petroleum probably was not formed in the pools where it is found today. As mentioned above, the deposits of crude petroleum were undoubtedly formed near scashores, but the action se rt Fie. 1-10, Typical oil-pool formations. In the center, pool water has forced the petroleum and gas up into a dome, or anticline, in the porous oil rock layer. Hard eap rock prevents the eseape of the oil. A fault, at the left, or a stratigraphic trap, as shown at the right, similarly traps oil pools between water under high pressure and hard rock strata. of the surrounding water gradually shifted the location of the oil pool. After a period of many centuries, the oil was forced through layers of porous rock strata until it finally became entrapped under a dome capped by hard rock. This made it impossible for the gas or oil to escape, and the water kept the pool of oil under pressure. A sketch of typical oil rock formations is shown in Fig. 1-10. Production of Crude Oil. In drilling for oil, the oil-retaining cap rock above the deposit is penetrated, and the existing pressure forces the oil, gas, and some water to the surface. An attempt is made to locate the bottom of the well at the richest part of the oil-bearing rock. This procedure makes it possible to keep out much of the water which would otherwise come up with the oil and gas. As the petroleum is removed from the underground deposit, the water moves in to take its place,16 FUELS AND COMBUSTION Eventually the natural pressure decreases to the point where it will no longer force the oil and gas to the surface. When this occurs, gas or water may be pumped back into the well to increase the pressure and force the crude oil from the pool. Under the natural pressure of the well, which may run to 1000 psi or higher, great quantities of hydrocarbon vapors are absorbed in the liquid petroleum and much liquid is held in suspension in the gases. As the crude oil and gas are pumped from the well, they are passed through a separator, or trap, where the liquid and the gases are separated. After a preliminary purification process in a field treating plant, the crude oil is pumped through pipe lines to the refinery. This treating plant reduces the dirt and water in the crude to less than 3 per cent so as to minimize pipe-line troubles. Fuel Chemistry. Any petroleum product is composed of a large num- ber of different hydrocarbon compounds, each of which has individual properties and characteristics. Fortunately, almost all the many hydrocarbons present in fuels may be classified into one of five chemical groups: the paraffins, isoparaffins, olefins, naphthenes, and aromatics. The chemical, physical, and com- bustion characteristics of a compound tend to be similar to those for the other compounds within the same group. Members of many other organic chemistry groups may be present in fuels in small amounts while others appear as intermediate products of combustion. Before we discuss the properties of any of the groups, a few terms com- mon to the chemistry of fuels should be mentioned. Carbon atoms have a valence of 4, while hydrogen atoms have a valence of 1. There is a tendency for the carbon to pick up other atoms until all four of its valence bonds are used, in which case the resulting compound is said to be saturated. Sometimes a carbon atom does not have all the other atoms it could hold, but two or more valence bonds are shared with another carbon atom. In this case the compound is said to be unsaturated because it is possible to add more atoms to the molecule. Hydrocarbons are known as chain compounds or ring compounds depending upon their molecular structure. Compounds of the same chemical group that have the same number of carbon and hydrogen atoms but different molecular structures are called isomers. Normal Paraffins. Normal, or straight-chain, paraffins are stable, saturated compounds having the general chemical formula CrHony2. The molecular structures of three of the members of the normal paraffin family are shown in Fig. 1-11. Each compound in this group has a name ending in -ane. The names of some of the compounds in the series with their formulas and a fewFUELS 17 physical properties appear in Table 1-7. Methane has one carbon atom in the molecule, formula CH,, and each member in the family has one more carbon atom in the molecule than the compound preceding it. A large portion of any hydrocarbon fuel is composed of normal paraffins. H HH HH H HHH HH HH HW wba nddddbsa wddddddita h Adak k Habhagh a Methane Pentane Octane Fra. 1-11, Molecular structures of three normal paraffins. Isoparaffins, Any compound with four or more carbon atoms may possess the same number of carbon and hydrogen atoms as a normal paraffin, but have them arranged in a different manner from that shown above. Thus octane, CsHys, may occur as a straight chain or in the more compact molecular structure shown in Fig. 1-12. The isoparaffins may carry the same names as the related normal paraffins with the prefix iso- being added, or they may be named by the number of carbon atoms occurring in the straight chain and the number, location, and name of attached groups. Thus, in Fig. 1-12, the 2, 2, 4 denotes that two methyl, CH, groups are attached to the second atom in the pentane straight chain, and one methyl group is attached to the fourth. There are still 8 H nt plant H-—C—C—C—C—C—H Mpa ya H—C—-H H—C—H yet Fie. 1-12, Molecular structure of isooctane (2,2,4-trimethylpentane).. carbon and 18 hydrogen atoms present in the molecule, hence this is an isooctane, an isomer of normal octane. It should be apparent there are many ways in which the molecular structure could occur for the larger, heavier molecules. Each isomer may differ only slightly from the others in physical and chemical characteristics, such as boiling point, specific gravity, or conductivity, but the combustion characteristics of the isomers may vary widely. For example, 2,2,4-trimethylpentane (isooctane) is a very smooth-burning fuel in a gasoline engine and hes been chosen as the standard for 100 octane gasoline. In contrast, normal octane is a rather poor engine fuel and has a low octane rating.18 FUELS AND COMBUSTION SSSRRAANARINS | SSSESSE eeasa: BELEATLAISIIT SG | a TRSESHe RESRSGN SESS | SO°RESN | aie =i ‘Tamie 1-7. Puorenrms or Sxuxcrep HypRocARRONS* g25b83 Name Family parafine aeDaratine and oo | Otefina ‘Aeobols UNIVERSI 26,04 Cate ‘Acetylene * Mort of those data were obtained from Selected Values of Properties of Hydrocarbons, Nat, Bur. lendarde, Cire. C401, API Research Project 44. Tnvaie, ates ‘Kectylene Latent heat of fuel at constant premure, 7 F KUT etme {FUELS 19 Olefins. Olefins are unsaturated paraffin compounds. ‘The maximum. amount of hydrogen is not present, which causes some carbon atoms to share two or more valence bonds. The members of this family have names similar to the paraffins except the suffix -ene is used. ‘The struc- ture of pentene is shown in Fig. 1-13. ‘The general formula for the mem- HH A n—6_-6-0=0-b_at Pyoi jy HHH HH Fro. 1-13. Molecular structure of the olefin, pentene, bers of this group is C,H2s. Olefins are formed principally in the refining process called cracking. As an example, when the heavy paraffin CisHa ia subjected to cracking, a reaction of the following nature may occur: CrsHa > Celis + CrHis Paraffin Paraffin Olefin The olefins, and the still more unsaturated diolefins C,H:,-2, are unstable compounds and are thought to be the cause of much gum forma- tion in gasoline. However, since they possess very good combustion characteristics, substantial quantities appear in modern high-octane gasolines. H oN AN “\ /* ale 4 _ i Fra, 1-14. Molecular structur thene, cyclopentai f'thenaph- Fro. 1-16, Molecular structure of the ‘romatic, benzene. Naphthenes. Naphthenes are saturated, stable compounds with a ring structure. Figure 1-14 shows the cyclopentane molecular structure. As can be seen from the figure, the naphthenes are saturated compounds even though the general chemical formula is C.H2,, the same as for the unsaturated olefins. This is because the ends of the chain are tied together. This reduces the potential of the carbon for taking on hydro- gen, ‘The names of the members of this family are the same as those of the corresponding paraffin except the prefix cyclo- is added to denote the ring structure of the naphthenes. ‘The physical properties of this group20 FUELS AND COMBUSTION are similar to those of the normal paraffins, but the combustion properties are more like those of the isoparaffins. Aromatics. The aromatics are unsaturated but stable ring compounds. Benzene, CH, is the most characteristic member of the group, and all aromatics consist of some variation of the benzene ring shown in Fig. 1-15. The general chemical formula for this group is C,H... An inspection of the figure shows benzene to be unsaturated. Unlike the olefins, there is no tendency for oxygen atoms to be picked up to take the place of the double bond. This group has very desirable combustion characteristics for use in spark-ignition engines, and members of the group are often added to gasoline to produce high-octane fuels. Composition of Crude Qils. Crude oil is a liquid consisting chiefly of hydrocarbons with traces of sulfur, nitrogen, oxygen, and a few impurities such as water and sediment. The chemical analyses of representative petroleums from various oil fields are shown in Table 1-8. ‘This shows that the percentages of carbon and hydrogen present in the crudes from all these sources are essentially the same. However, an analysis which shows merely the percentage of each element in the crude oil is somewhat misleading. When the crudes are analyzed on the basis of the hydro carbon families present and the amounts of the different compounds in those families,.it is found that oils from the different sources vary considerably. Tapue 1-8. Typtcan Avatyses oF REPRESENTATIVE Caupe.Oms Per cent, by weight Source | Cason | Hydrogen | EMP, easing Poonyivanin & | ou 1 West Virginia. 84 3 | 3 Ohio. 84 13 3 California. 82 10 8 ‘Texas, 85 ul 4 Mexico 84 10 6 Ronin, Bake | 2 1 1 Petroleum from the Pennsylvania fields is composed principally of pardffin hydrocarbons and yields what are known as “paraffin-base” products. Crudes from the west coast area contain a larger percentage of naphthenes than the Pennsylvania oils and hence are termed “naph- thene-base,” or sometimes “asphalt-base,” crude oils. Even in west coast crudes the largest percentage of compounds may belong in theFUELS 21 paraffin family, but the number of naphthenes present is much greater than in the Pennsylvania petroleums. Oils from the Texas-Oklahoma area, commonly called mid-continent oils, are known as “‘intermediate- base” crudes because their composition is between that of the paraffin- base and the naphthene-base crudes. Crude oils from other fields throughout the world are usually classified as belonging to one of these three types. eo réceston ator mere tens ban es Comet ws atone Setar tener cnt aie ct Fie. 1-16. Flow diagram of a petroloum refinery. (After API.) Refining of Petroleum. ‘The refining of petroleum is one of the most advanced of modern industrial techniques. In the fractional distillation process, crude oil is separated into many parts, these fractions are treated and further processed, and the final products of gasoline, fuel oil, ete., are obtained by blending proper amounts of the refined fractions. Since petroleum consists of hydrogen and carbon compounds, refining processes involve the separation of the light compounds from the heavy, and the conversion of one hydrocarbon compound to another. ‘The refining technique has been so perfected that it is now possible to form22, FUELS AND COMBUSTION almost any product from any crude oil in the desired proportions, although in many cases it would not be economical A few of the fundamental processes employed in modern refineries are described in the paragraphs which follow. A simplified flow diagram showing where each process fits into the over-all produetion is given in Fig. 1-16. Fractional Distillation. The first step in the refining of crude oil is the fractional distillation process, Primary fractions, obtained from a frac- tionating tower, and the order in which they occur are shown diagram- matically in Fig. 1-17. In this simplified representation of the process, Fig, 1-17, Straight-run fractions obtained from the fractional distillation process. liquid petroleum is heated to a temperature of about 700 F in a tube heater, which evaporates most of the crude oil. The vapors are passed into the fractionating column where the oil is separated into several fractions. The heavier compounds have a high boiling point and, as the vapors rise in the tower and are cooled, the heavy fractions precipitate first and are removed from the tower. The light hydrocarbons rise to the top of the column before condensing, while compounds with inter- mediate boiling points are removed at the intervening stages. The liquids obtained from the various stages of the distillation process are known as straight-run, or primary, fractions. In the refinery, fractional distillation is carried out in two or more towers, either at atmospheric pressure or in a high vacuum. Sometimes the straight-run fractions can be used as they are, but usu- ally they are improved by further treating. ‘These fractions provide the charging stock for the other refining processes where the nature of eachFUELS 23 fraction may be completely changed to increase the yield of a specific product. Cracking Process. A hydrocarbon fraction such as heavy gas oil ean be broken down into a number of lighter fractions by a process known as cracking. This process makes it possible to increase the yield of gasoline or light fuel oil per barrel of crude. The thermal cracking process is accomplished by subjecting the gas oil to temperatures of 1000 F or over and pressures of 1000 to 1500 psi. Under these conditions, the heavy hydrocarbon compounds are broken to form new compounds, some lighter and some heavier than the originals. Many of the lighter com- pounds fall into the range for gasolines and light fuel oils. A few are too light to condense at atmospheric temperature, and they form refinery gases which must be further processed. The heavy residues are used to form coke or some other by-product. Cracking may be achieved at lower temperatures and pressures if a suitable catalyst is present. There are a number of commercial catalytic cracking processes developed, using various catalysts, which give a higher yield of premium gasoline from the heavy fractions than the thermal method. Polymerization, Light hydrocarbon gases resulting from the frac- tional distillation or cracking processes may be built up into heavier compounds by a process of polymerization. Thus, many gaseous prod- ucts of the refinery are utilized which might otherwise be wasted. Asan example of the type of reaction followed here, many light compounds, such as CH,, CsH,, CsH« and CsHs, may be polymerized, or joined together, to form heavier molecules such as Ces, OsHss, and CsHus. The initial and the final compounds may be members of the normal- paraffin, isoparaffin, olefin, naphthene, or aromatic families, depending upon the reactions followed. The products from the polymerization reaction are controlled by regulating the temperature and pressure, and by the catalyst used in the process. ‘Absorption Process. The gases leaving the oil well and also many from the refinery processes contain heavier hydrocarbons in the vapor state. A portion of these heavier hydrocarbons fall into the gasoline range. The absorption process is used to recover these vapors. In this Process the gases come into contact with a kerosene or light oil which absorbs the heavy hydrocarbon vapors but not the lighter hydrocarbons making up the gas. The vapors are then removed from the absorbing oil by heating the latter in a steam stripper and driving off the absorbed vapors. In some cases, part of the heavy vapor is precipitated by flow- ing the natural gas past refrigerating coils before sending it through the absorption process. If the natural gas is compressed at the well before entering the pipe lines, much of the vapor may be precipitated at that24 FUELS AND COMBUSTION point. The liquid obtained from natural gas by precipitation, or by absorption, is known as natural gasoline. Propane and butane are removed from natural gas by an absorption process and are bottled for commercial sale or blended with other petro- leum fractions to increase the volatility of those products. Hydrogenation. ‘The process hydrogenation may be described as a cracking process which occurs in an atmosphere of hydrogen. Here cer- F left, an Standard Oil Co., N. J.3 photo by Libsohn.) tain unsaturated compounds pick up more hydrogen to become saturated, and the yield and quality of gasoline are again increased. ‘Temperatures in this reaction are controlled at approximately 750 to 1000 F while the hydrogen pressure is held between 300 and 3000 psi. ‘This process gives a high-octane product with a high boiling point and high flash point, especially suited for aviation gasoline. Alkylation, Light undesirable hydrocarbons of one chemical famil may be reformed to heavier compounds of another family by a process known as alkylation. Thus, light olefins and isoparaffins, such as butyl-FUELS 25 ene, propylene, and isobutane, are fed into a reactor which converts them into isoparaffins having a boiling point which falls into the gasoline range. Here again is a process which produces a high-octane fuel having a high boiling point and low vapor pressure. Finished Blended Products. ‘The produets from the various refinery processes are blended together to form liquid fuels with the proper 109) D aromatic ss ONaphthene ring ste chin = 40806070 «80D O Fraction number 400 70 300 B50 500 Evoporation temperature, F Fa, Distribution of hydrocarb na straight-run mid-continent gaa oil by boiling point. (Ward and Smith, presented before the Western Petroleum Refiners’ Association, San Antonio, April, 1951.) physical characteristies to give high-quality gasoline, fuel oil, kerosene, diesel fuel, ete. Also these liquid products may be put through various finishing processes to reduce the sulfur and wax contents, inhibit later gum formation during storage, etc. Each of these fuels contains hun- dreds of different compounds belonging to each of the five principal hydro- carbon families. Although there are many tests for determining the physical properties of liquid fuels which are discussed more thoroughly in Chap. 5, the greatest change in the physical characteristics of the different liquid fuels is their volatility. Gasoline is composed of a large26 FUELS AND COMBUSTION number of hydrocarbons containing molecules with 5, 6, 7, and 8 carbon atoms to the molecule which tend to vaporize readily. Kerosene is some- what less volatile and contains a greater number of heavier hydrocarbons. The heavy fuel oils and diesel fuels are composed principally of hydro- carbons with 12 to 16 or more carbon atoms to the molecule, and as a result they have much higher evaporation temperatures than gasoline. Figure 1-19 shows the composition of the various hydrocarbon fractions which have been determined in a straight-run gas oil used as diesel fuel. The exact and complete analysis of such a fuel is impossible, but many hydrocarbons can be detected positively, and the presence of many more can be established quite definitely. For the purpose of analyzing the oxygen requirements for combustion, the analysis of a liquid fuel may be given as: 1. Percentage of hydrogen and carbon by weight 2. Ratio of hydrogen to carbon by weight 3. Ratio of the number of hydrogen atoms to the number of carbon atoms in the fuel. Note that none of these methods attempts to show all the constituent hydrocarbons, but only the hydrogen and carbon contents. Since these fuels are composed of so many compounds, any formula given to repre- sent the liquid would be merely an average of all the formulas of the com- pounds making up the fuel. All gasolines are approximately 85.7 per cent carbon and 14.3 per cent hydrogen by weight and may be represented quite accurately by the average molecular formula CsHis. Most kerosene similarly is 85.7 per cent hydrogen and 14.3 per cent carbon by weight and the formula Ci.oHas2 represents all kerosenes. Light and heavy diesel oils and fuel oils will vary from about 14 to 15 per cent hydrogen. ‘The average formula for such heavy fuels may vary widely. GASEOUS FUELS Gaseous fuels enjoy a number of advantages over solid and liquid fuels for many applications. ‘They may be easily piped into a furnace so that, no physical handling of the fuel is necessary. Generally, gases are free from ash or other foreign matter, and they burn completely. Also, the control of gas flames is relatively easy, and complete combustion with no smoke can be obtained with a low percentage of excess air. In addition to these advantages, in many parts of the country today, gaseous fuels compare favorably in cost per Btu to either coal or oil; in many instances, gas is the cheapest. One of the disadvantages in the use of gas is the difficulty in storingFUELS 27 any appreciable supply. Large gas holders which store several million cubic feet of gas under high pressure are used, but even this is not com- parable to the ease of storing large supplies of solid and liquid fuels. Brief descriptions of the common gaseous fuels used commercially in this country appear in the paragraphs which follow. Table 1-9 gives typical analyses of the components, specific gravities, and heating values of these gases. ‘The specific gravity of a gas is the ratio of the density of the gas to the density of air at the same temperature and pressure. Heating values of gases are reported at 60 F and 30 in. Hg, the standard adopted by the American Gas Association (AGA) for that purpose. Natural Gas. Of the various gases listed, natural gas is used far more widely than any of the others. It is compressed to pressures of several hundred pounds per square inch and sent through pipe lines from the oil fields of Texas, Louisiana, and Oklahoma to areas in the north central and northeast portions of the United States. Much of the western United States is supplied with natural gas from wells in that area, while oil fields in Pennsylvania and West Virginia have supplied local areas with gas for many years. ‘Natural gas is a nearly odorless and colorless gas that accumulates in the upper parts of oil or gas wells. It consists chiefly of methane, CH, with varying quantities of heavier hydrocarbons, and has a heating value between 1000 and 1100 Btu/cu ft. ‘The gas may contain small amounts of noncombustible constituents such as carbon dioxide, nitrogen, and water vapor. - Like petroleum, natural gases from any given region of the country have certain characteristic analyses. Gases in the east, or Appalachian region, are usually high in paraffin content. Western gases contain relatively higher percentages of carbon dioxide. Nitrogen and some helium charac- terize the natural gases from the Kansas, Oklahoma, and Texas regions. In this country, no natural gas contains carbon monoxide, hydrogen, or olefin hydrocarbons in any appreciable amounts. Some fields produce gases containing hydrogen sulfide, H:8. Because of their pungent odor such gases are called “sour” natural gases. They may be“sweetened” by removing the hydrogen sulfide. Much of the gas leaving the liquid and gas separator at the oil well still contains appreciable portions of liquid hydrocarbons in the vapor phase. “Dry” natural gas contains less than 0.1 gal of gasoline per 1000 eu ft of gas. The higher hydrocarbons in “wet” gas are mostly propane, butane, and pentane, although a small percentage of still heavier compounds may be present at atmospheric pressure and normal temperatures. The natural gasoline obtained at the well, by compressing and cooling the gas to condense the higher hydrocarbons, is often termed casing-head gasoline.FUELS AND COMBUSTION 28 FH OE PE LODIVI MON MAIO MO} “shar "soneoery wep ng snooeen Te | 069 B20 ri 10 22] It mR Lt | OFS jeo'o) FZT re |e-oleo mq ya! “soyem poyounquog, 19% | 082 jgo-o| a8 @t|6°0|o'9 Wo Savoy soq8M poyaunquy, toy | 982 feo] 1-9 ¢|roloe 818 MOY oye poraunqss) eez | 092 ozo 20 wl6o|e's smourunyig, (se 1oyem) 908 ony zoz | 18% |z9°0) 8 {Lolrs 2400 (sul sje) se onigl “0g, 2 ee oo] Jerr . -2OUULNS ASU, “BT es1 e918 | 0s] 0°0 Je"¥ ~-sgonporg eI gh 980) | 05] 1-0 0's ayonsyauy ~aoonpoag 60 | 608 i 0) 0 | 8 |e ole sompoxd-sg wan O40) sor | oes ero] Fe ¥ [Folts Hoyo: (wo, 08 1909) “St ors, 669 FO] FE | 8/80/21 ‘sud wo “pT 98F | cS Bro] Of SO] z | wor muozuoyy 503 [WO “ET org | og ze°0) ore | volet paved 08 LO “EL SLVI 68°0| 9°68 Z'0|e'0 | “yoss0 oswyd “ce no Asouyot “Tt U zo “yow9 aseyd “Dey Ho Avouyou “OL a 99 Joe Bua Asay auing “6 z ¥6 [0°9 | sul rounyuy ouving “g 1 “0 lea low | suit Krouyoyy ouedosd “Z . -o jessie | | su jeanquy | oundosg “9 * PPL [oes [oF ad&y pwoy-Burse) renqeN “g ve ¥ 8 | [so on ‘1p swear SeyumeN p oor eo “eaMQUN *. set go | | rsa seaings yaa spamy = les Lol prs | “py “wuysurwarsy | TenQUN “TE | ih 'H’O |°H'OPH'O | "HO | #H | 00 | §N | *0 FOO somog edt poe zoquruy, SSIBVD TAN 40 SASATVNY TWOLEAL, “6-1 STAY,FUELS 29 Liquefied Petroleum Gas. In the processing of petroleum, considerable quantities of propane and butane are produced. ‘These gases can be liquefied at normal temperatures by subjecting them to a moderate pres- sure. They are liquefied and either “bottled” in steel cylinders at the refinery or shipped in large bulk-type pressure tanks for later redistribu- tion, ‘The recent increase in the use of these gases is due largely to their flexibility in handling and storage. Liquefied petroleum gases are used as stand-by supplies for users of natural or manufactured gas, also to aug- ment the heating values of some manufactured gases, and as fuel forstoves, trucks, busses, and tractors in many parts of the country. Special precautions must be taken in using propane and butane because of two physical characteristics not found in the other gaseous fuels: (1) Because of their high heating value (approximately 2550 Btu/cu ft for propane and 3200 Btu/cu ft for butane), burners must be specially adjusted to use them. (2) Since propane and butane are heavier than air, escaping gas will tend to settle and collect in pockets thus creating an explosion hazard, Refinery Oil Gas. During the many operations involved in the refining of crude oil, light gases are produced which cannot economically be con- verted into gasoline or some other liquid product. These gases are termed refinery oil gases and consist of various light hydrocarbons with small percentages of hydrogen and carbon monoxide present. It is not common to pipe these gases any great distance for distribution, but they are generally used within the plant to help supply fuel for the many furnaces and heaters required in a refinery operation. Coal Gas. The oldest method of manufacturing gas is the high-tem- perature coal-carbonization process. ‘This is still used to produce a large proportion of the manufactured gas distributed in cities and towns for domestic and industrial use today. Coal gas is produced in horizontal, inclined, or vertical retorts in which the primary product is gas; and coke, which is the secondary product, is below average grade and not satis- factory for metallurgical use. ‘The retorts are fired either intermittently or continuously, depending on the design, with high-volatile coals which will give a high gas yield. Coal is heated to temperatures up to 2700 F in the presence of very little air. The retorts are heated generally by burning producer gas in grill work or chambers surrounding the charge of coal, although some of the coal gas itself may be fed back into the unit to help maintain the necessary high temperatures. The complex organic compounds of the coal decompose at the high temperature and form simpler, volatile prod- ucts and coke. The composition of the coal-gas product is controlled by the size of charge, the temperatures employed during the carboniza-FUELS 31 gas may be increased by spraying steam into the coke charge of the gas producer occasionally. The steam reacts with the coke to form carbon monoxide and hydrogen. ‘The addition of steam to the process must. be employed only intermittently, since this reaction absorbs a considerable quantity of heat and may cool the coke bed to the point where all reac- tions will cease. The low heating value of producer gas does not make distribution of this gas in long pipe lines feasible. It is used extensively for firing open Coal in, Producer gas ou, intermittenty ‘contnucusly ¥ Fra. 1-20, Diagram of a gas producer. hearth furnaces in the steel industry. It may be used hot just as it comes from the gas generator, or the tar and other impurities may be “scrubbed cut.” Recent research indicates that the use of small, efficient, high- output gas producers may be a feasible way of utilizing coal, while still maintaining many of the advantages of burning gaseous fuel in com- bustion equipment. Blast-furnace Gas. Blast-furnace gas is one of the by-products of the blast furnace operation. It contains a large per cent of nitrogen and has the lowest heating value of any of the commercial gases. The Btu per cubic foot of blast-furnace gas frequently runs below 100. For this reason it is used near the area in which it is produced to operate gas ‘engines, to heat by-product coke ovens, and for various heating processes.32 FUELS AND COMBUSTION Carbureted Water Gas. ‘The manufactured gas produced most widely for commercial distribution is earbureted water gas. Figure 1-21 shows a diagrammatic view of a generator to produce such a product. ‘The charge of coal or coke is heated to incandescence by burning the coal vigorously during the “blow” run when air is blown through the fuel bed. After the coal charge has burned and has been heated sufficiently, the air supply is shut off. Steam is then forced either up or down through the bed of hot coke during the “make” run, and water gas, or blue gas, is generated by the reaction of the water with the hot carbon according to Waste gas from ‘lost run Steam for pron Ai for blest run Fria. 1-21, Diagram of a carbureted craters gonoraor. the equation: H,O + C—+CO+H:. This reaction cools the charge within 3 or 4 min. Then the “make” run is stopped, and more air is forced through the fuel bed to burn and thus heat the coke during another “blow” run, ‘Thus, very little nitrogen is included in the finished water gas generated during the “make” run, because air is not admitted to the fuel bed during that period. Part of the volatile matter of the coal is included in the product gas, however. Because of the high carbon monoxide content of the gas, which burns with a short, blue flame, water gas is often called blue gas. The heating value of blue gas is approximately 270 Btu/cu ft, as itFUELS 33 comes from the gas generator. For commercial distribution, it is desir- able to have product with a higher heating value. The increase in Btu value is achieved by enriching the water gas with gas oil (or fuel oil) by spraying the liquid oil onto a checkerwork of heated firebrick, called a carburetor. Sometimes the oil is sprayed into the fuel bed of the gas generator itself. The intense heat cracks the heavier hydrocarbons of the gas oil into lighter hydrocarbons which remain in the vapor phase in the carbureted water gas. ‘The heating value of this product could be maintained at almost any value by regulating the amount of gas oil added in the carburetor, but values of 500 to 600 Btu/ecu ft are common. Sewage Gas. The decomposition of sewage sludges produces a gas that is approximately two-thirds methane and one-third carbon dioxide. Heating values of the gas vary from 600 to 750 Btu/cu ft. The amount of this gas produced in normal sewage-disposal plant operations varies from 0.3 to 1.0 cu ft per capita of population per day. Sewage gas is seldom distributed commercially but is used to supply heat and power to operate city sewage-disposal plants. SYNTHETIC FUELS The obvious unbalance between the use of liquid and gaseous fuels and their reserves, as compared to the use and reserves of coal, has caused much concern as to what other fuel sources might provide suitable sup- plies of liquid and gaseous fuels to meet future demands. This specula~ tion seemed especially urgent during times of temporary petroleum shortages such as were experienced in 1918-1919 and 1945-1947. Follow- ing each of these periods, new reserves of crude oil were discovered, and new production and refining methods have enabled the supply of liquid fuels from petroleum to more than meet the demand. However, research departments of various private corporations and the United States government have continued investigations of possible sub- stitutes for petroleum products. Some of the developments receiving the widest attention and showing more or less promise are discussed here. Oil Shale. The reserves of oil shale are large in many states of the union, especially in Colorado. It is estimated that at least 100 billion barrels of oil can be obtained from known United States deposits of oil shale. The U.S. Bureau of Mines has established a pilot plant at Rifle, Colo. to investigate and develop a method for recovering this oil. Oil shale is a rock bearing anywhere from 7 to 50 gal of oil per ton of shale. The quantity of liquid is so low that it cannot be forced from the rock by pumping it from the ground as is done with oil-bearing sands. Neither will a high pressure exerted on the shale by water or mud displace the oil. The production of liquid fuels from oil shale may be divided into twoFUELS 35 diagram of one of these. This portrays the Fischer-Tropsch method which has been used extensively in other countries during the past decade. Basically, the process involves the forming of a synthesis gas in a gas producer by partially burning coal with insufficient air. This yields a product high in CO and H: content. The synthesis gas is then passed through a synthesis reactor where, in the presence of a catalyst and the proper temperature and pressure, the CO and Hz are reformed to hydro- Fluid—fuel-bed ‘coal combustion chamber SYNTHESIS -GAS GENERATION AND PURIFICATION Hydrocarbons, [—__]} Fue! gas C38Cg[ Poymer LT Light Polymer Bre re 138s Biot Product ‘Heavy polymer be or os |" eee ES Steom ter oil Heavier Heavy gos oil Fro. 1-28, Liquid fuels from synthesis of coal. carbons of the paraffin, olefin, and alcohol families. ‘These products are further refined by conventional processes to form suitable liquid fuels. The Bergius hydrogenation process is another means for converting coal into liquid fuels. It employs a hydrogenation process on a powdered coal paste. The U.S. Bureau of Mines has established a pilot plant for investigation of all phases of coal synthesis at Louisiana, Mo. Synthesis of Natural Gas. A synthetic gasoline can be produced from natural gas using much the same process as that described for the syn- thesis of oil from coal. In both of these processes, a low-percentage Btu36 FUELS AND COMBUSTION conversion is obtained since part of the original coal or gas must be burned to form the synthesis gas. ‘The production of liquid fuels from natural gas is reported to be able to compete economically with the production of petroleum fuels. Unfortunately, the reserves of natural gas are small as compared to those of oil shale and coal, so that the latter seem to offer the best possibility for supplying unlimited quantities of liquid fuels for many years. Alcohol and Vegetable Oils. The U.S. Department of Agriculture has established a pilot plant at Peoria, Ill, to investigate the possibility of producing liquid fuels from agricultural products. ‘These fuels might take the form of natural oils, such as corn oil, cottonseed, or peanut oil, or alcohols formed from organic compounds. While these compounds have a few select uses at the present, no means seem in sight for processing a satisfactory fuel in any form from agricultural products which can begin to compete economically with present fuels. ‘Underground Gasification of Coal. Attempts are being made to gasify coal underground and bring up much of the heat content without mining the coal. Tests have been made to study the feasibility of this plan at Gorgas, Ala., under the sponsorship of the Alabama Power and Light Co. and in cooperation with the U.S. Bureau of Mines. Similar tests have been and are being made in other countries. ‘The general plan is to force air or oxygen into an enclosed vein of burn- ing coal, let the ground act as a gas producer, and take the product gas out of the mine a few hundred feet down the vein from the point of the admission of air. So far it has been proved that the coal will burn, and rather completely, under such circumstances. The results obtained by the end of the second Gorgas test in 1950, however, were not. too encour- aging in that a gas low in Btu content was produced. At any rate, here is a possible new development which would throw many new factors into the economics of the use of fuels and power generation. Problems 1. Distinguish betwoen proved reserves and estimates of fuels, 2. Why is sulfur listed separately when a proximate analysis is reported? 3. Correlate the percentages of volatile matter and fixed carbon for the various ranks of coal. 4. In general, what conclusion may be drawn in regard to the effect of the compos tion on the heating value on a dry basis for solid fuels? 6. Why is there less difference between the fixed carbon in the proximate analysis and the carbon in the ultimate analysis for a high-rank than for a low-rank coal? 6. Discuss the economics of the hypothetical problem: What would happen if Pennsylvania, West Virginia, Kentucky, and Ohio should suddenly be depleted of their coal resources? 7. Compare the origin of coal to the origin of petroleum