The Cannel Coal Industry of Kentucky
Transcription
The Cannel Coal Industry of Kentucky
Energeia Home Vol. 7, No. 1, 1996 The Cannel Coal Industry of Kentucky: A Brief History of Resource Development and Depletion James C. Hower, Center for Applied Energy Research INTRODUCTION The mining of cannel coal was a small, but prestigious, component of coal production of Kentucky in the 1800s and early 1900s. Cannel coal sold for about $2.50/ton (at the mine) at a time when bituminous coal sold for less than $1.00/ton. Kentucky cannel coals were marketed throughout the United States and Canada, as well as to Europe and South America. Perhaps the most unusual marketing of Kentucky cannel occurred at the 1893 Columbian Exposition at the Chicago Worlds Fair where a 23 foot by 27 foot cannel arch was constructed, modeled after the Arc de Triomphe. Cannel coal was retorted into liquid fuel, gasified as an enricher of municipal gas supplies, and distilled as a feedstock for the production of chemicals. Each peak in usage was subsequently tempered by a discovery of cheaper sources of liquid hydrocarbons. The production of cannel, as with any mineral commodity, was at the mercy of market demands and available transportation. Cannel coal, more than banded bituminous coal, occurs in relatively limited areas, leading to the rapid exhaustion of commercial deposits as well as the failed attempts of investors to develop deposits that did not attain commercial size. This history of the Kentucky cannel industry provides a view of a limited resource, in many cases, mined to exhaustion, with a rather specialized market. In some respects, the history of the boom and bust years of the cannel industry is similar to the development of the coal industry on the whole. The latters resources are not as limited but they are, nevertheless, exhaustible. Furthermore, without a market and available transportation to get the coal from the mine to market, the resource will remain unmined. Brief histories of two of the more important deposits serve to illustrate the history of the repeated rise and fall of the cannel coal industry. The Breckenridge deposit in Hancock County, Western Kentucky, and the Morgan County deposits, Eastern Kentucky, will serve as mirrors on an industry that was important in its own right but, overall, was obscured by the larger bituminous mining industry. CASE HISTORIES Breckenridge The Breckenridge cannel coal, from southern Hancock County in Western Kentucky, ranks as Kentuckys most famous cannel. Owing to its outstanding quality, which surpassed that of the Scottish Torbanehill cannels, it is still among the best known cannels in the (continued, page 2) Evolution of PYROGRAF IIITM: Process Produces Vapor-Grown Carbon Fibers Using Coal Bob Alig Applied Sciences, Inc. Hydrogen sulfide has made it possible to produce vapor grown carbon fiber in practical quantities. Coal could eliminate the need for handling toxic Hydrogen sulfide at an acceptable price. Furthermore, this could potentially resolve emission problems and transform high-sulfur coal into a very desirable commodity. Introduction A miner returning home from the coal mine, photo by Russell Lee, University of Kentucky Photographic Archives The basic process for producing vapor grown carbon fibers was developed by Dr. Gary Tibbetts at the General Motors NAO Research Labs and described in ENERGEIA, Vol. 1, No. 4, 1990. In this process, an organometallic compound containing iron is injected into a hydrocarbon vapor at temperatures above 1000 °C. The fibers lengthen and thicken as they move through the reactor with the gas stream and col(continued, page 3) Cannel Coal, (continued) world. Local legend traces the discovery of the deposit to two hunters who found the cannel at the outcrop and proceeded to build a cabin and fireplace with the coal. The first local use of cannel as a building stone failed. cannel as a fireplace coal. The mine site is now a private hunting club. Morgan County In the second decade of the 20th century, Kentucky was considered to be the premier cannel-producing state. Morgan County led Kentucky with production surpassing the total of any other state, probably surpassing the production from the Breckenridge mines (which, pre-dating Kentucky Department of Mines and Minerals records, is inaccurately known). Completion of the link was delayed by the 1899 Kentucky River floods that washed away the rail bridge. A rail link to Morehead eventually served operations on the north side of the county. The Kentucky Block Cannel Coal Co. was the largest producer, generally producing 5-10 times the cannel as its nearest competitor. The company also developed oil and gas wells on its Cannel City property in southern Morgan County. The development of the Breckenridge deposit dates to at least 1837 when it was sold for the use of Ohio River steamers at a price equivalent to $2.50/ton. In the 1850s, the Breckenridge deposit was The principal cannel coal mined, developed first as an exportable commodmarketed as the Pluto cannel, and a In 1892, however, Morgan County was ity and, later, as a source of liquid fuel. In thinner cannel were marketed as remote and the cannel resources were the early 1850s, the cannel was sold for domestic fuel, gas enrichers, and for the totally undeveloped. Lacking, also, was up to $15/ton in New York and London production of cannel-oil by-products. transportation. Morgan County is on for use as a gas enricher. Up to 10,000 During the World War I era, the the Licking River, and did not have the tons/month were shipped to England, chemical industry, which had become railroad access of the Big Sandy, doubling as ballast for the ships. The increasingly dependant upon a crudeexport market oil feedstock, faced ended in about 1856 wartime shortages. with the construcCannel oil and coal tion of 30 retorts tars from coking were for coal oil refining. two of the alternative The Breckenridge feedstocks used. Coal & Oil Company Postwar industrial operation was one growth maintained of 55 coal-oil compathe demand for nies operating in cannel, leading to the United States then-record producin 1860. The discovtion in Morgan ery of petroleum in County in 1920. The Western Pennsylvacannel boom colnia the previous lapsed in 1921, year and the production decreasing subsequent decline by an order of in oil prices to magnitude, as the $0.52/barrel in 1861 early development of Map indicates Kentucky cannel deposits discussed. Dotted lines refer to the killed the coal-oil the Persian Gulf oil Eastern and Western Kentucky coal field boundaries. industry. Most of fields and the domesthe retorts in the US, tic oil transportation Cumberland, or the Kentucky River many of which had been based on networks reduced the desirability of valleys, all sites of earlier mining Breckenridge cannel, were converted to using a solid fuel to produce a liquid development. The nearest railroad, the crude-oil refining. product. Newport News and Mississippi Valley, Mining resumed in the 1880s and A second boom in production followed was at Morehead, Rowan County, markets were found throughout the World War II. In the face of a rapid rise requiring an 18-20 mile rail extension. United States and as far away as Nova in oil prices fueled by the increased Scotia and Chile. The revival did not Production was anticipated by 1894 but transportation and industrial demands, last as the reserves were depleted to the . . . the building of the necessary the US government funded shale- and point where the mining production fell railroad, the prospects for which were coal-conversion projects in the late to 300-400 tons/month in 1896, the so promising early in the year, failed 1940s. Again, the development of equivalent of one days production in through unexpected difficulties Persian Gulf oil fields, offshore petro1887. Underground mining ended in (Norwood and Grider, 1894, KDMM leum resources in the Gulf of Mexico, November 1898, a victim of the market report). Morgan County finally and improved oil transportation disruptions caused by the Spanishentered commercial production in 1901 networks effectively killed any hope of American War, armed conflict with a with the Caney Cannel mine (Biggstaff developing a synthetic-fuel industry. major customer never being good for Cannel Coal Co.) and the Kentucky The most recent cannel mining in business. John Taulbee from Morgan Block Cannel mine (Kentucky Block Morgan County, with the intended County owned the deposit from about Cannel Coal Co., New York City). The market being home heating in Ireland, 1904 to his death in the early 1970s. He final rail connection was the Ohio and was abandoned after mining a few attempted to mine the deposit but was Kentucky Railroad covering 27 miles hundred tons. For the first time since unsuccessful. The next owner, John between Caney (Morgan County) and the beginning of cannel mining, Corder, did surface mine the remains of Jackson (Breathitt County) on the Morgan County produced no coal, the underground works in 1977, with Kentucky River where it connected cannel or bituminous, in 1994. his Warm Glow Coal Co. marketing the with the Lexington & Eastern Railroad. (continued, page 3) 2 Cannel Coal, (continued) PYROGRAF IIITM, (continued) SUMMARY lected as they exit. Precise control of the hydrocarbon and ferrocene or iron pentacarbonyl flow rates is necessary to achieve optimum growth. This fiber was known as PYROGRAF IITM. However, the process was non-productive; the iron catalyst did not grow filaments profusely enough to be a practical continuous reactor. From these initial developments at General Motors, a joint venture collaboration was entered into with Applied Sciences, Inc. in 1992 for further development and manufacture. The cannel industry in Kentucky garnered prestige far beyond its contribution to the total coal production of the commonwealth. Cannel production compared with bituminous production peaked at 2.2% in 1895. By the time Morgan County came into full production in 1902, cannel production was only 1% of bituminous production. Cannel filled a niche market as a specialty fuel. When those markets were serviced by cheaper, more convenient fuels, the market for cannel diminished. The coming of pulverizedfuel combustion, as opposed to stokerfired combustion that could handle larger particle sizes, placed greater value on the easier-pulverized bituminous coals, further displacing the extraordinarily hard, although higher heating value, cannel coals. Despite the dreams of investors, who still, at times when synthetic fuels may be approaching economic viability, hope to exploit cannels for their inherent high retortable oil content, cannel can now be best described as a novelty fuel. Considering the limited extent of cannel deposits and the nearexhaustion of the best deposits, the absence of a market for cannel in the utility sector, and the persistent future development of synthetic fuels (in which cannel, for the first reason cited, would not play a significant role), cannel use is not likely to expand beyond its current domestic markets. Although there was only a limited production of cannel, lessons from its history can be applied to the coal industry as a whole. Cannel was a desired commodity, leading companies to develop resources which, owing to the limited nature of the deposits, were not able to support the market demand for the product. Prior to that point, the cannel could not be developed before rail transportation from the mine to the market was in place. Ultimately, cannel was displaced by cheaper, more easily transported fuels, losing the extensive market it had gathered through the late 1800s and early 1900s. A version of this article first appeared in Uncertain and treacherous: the cannel coal industry in Kentucky, which appeared in the journal, Nonrenewable Resources, v. 4, p. 310-324, 1995. Dr. Hower is the senior coal petrographer at the CAER. He has been with the center since 1978. Sulfur Innovation A breakthrough occurred when it was found that sulfur was vital to fiber formation. Adding hydrogen sulfide (H 2S) at an equimolar level with the iron catalyst, vastly increases the filament formation as shown in Figure 1. This made it possible to proceed and develop the concept of a continuous reactor. The sparse fiber in the photo without sulfur clearly illustrates the need for sulfur. We believe that the sulfur becomes involved as a eutectic and is incorporated in the fiber by being adsorbed onto the catalyst, and subsequently overcoated with graphite. Furthermore, excess sulfur up to 12 times the S/Fe molar ratio still produces good fiber, but gradually develops a shorter, jagged structure at higher ratios. PYROGRAF IIITM Figure 2 shows scanning electron micrographs of vapor grown carbon fiber made using sulfur in comparison with typical commercial carbon fibers. The diameter of this fiber, known as PYROGRAF IIITM, generally averages 0.2µ as produced, while commercial fibers are 8µ in diameter. Due to the random distribution of the catalyst during fiber formation, the fibers become entangled during growth and are not in continuous lengths like commercial fibers. The length/diameter ratio for PYROGRAF IIITM ranges from 40 to 200. Due to the process, the material can be highly graphitized as it is made as shown in Table 1, which is similar or higher than heat treated, commercial carbon fibers. 10µm a a 10µm b Figure 2. Typical commercial fibers (a) in comparison with vapor grown carbon fiber using sulfur (b). b Table 1. X-Ray Diffraction Analysis Heat Fiber Treat (°C) Type c 4µm Figure 1. Effect of H2S on fiber growth. (a) no H 2S flow (b) at equimolar levels (c) at 17:1 ratio. 3 D-Spacing gp (nm) (%) As-grown VGCF 1300 ex-PAN As-grown Coal & Methane As-grown Coal only 2500 ex-PAN 2500 VGCF As-grown PYROGRAFIII -P-120 .34490 .354 .3459 ---- .3459 .342 .3377 .3385 .3378 -23 73 64 72 (continued, page 4) PYROGRAF IIITM, (continued) Hydrogen sulfide Most of the PYROGRAF IIITM made to date has used laboratory grade methane as a hydrocarbon source to assure reproducible results. Since one reactor can now produce almost a pound per hour, natural gas is frequently used and the hydrocarbon variations do not affect the output. A pound of fiber made with laboratory grade methane adds $70 to the cost as compared to $0.44 for natural gas. Although the addition of H2S was instrumental in achieving this improvement, it was used with great reluctance. Hydrogen sulfide is expensive, highly corrosive, flammable, and its toxicity is commensurate with hydrogen cyanide. Suppliers are hesitant to ship the material and prefer to ship H2S that has been diluted in CH4 to the 1 to 3% level at an astronomical cost. Since coal contains many compounds of sulfur and all may not participate in the reaction, a 1.6 ratio was chosen that was higher than the usual control formulations with a 1.0 H2S/Fe[CO]5 molar ratio. Ohio #8 Coal from CONSOL Inc., at 4.71% total sulfur and 46.6% total carbon, was pulverized to less than 63µ. Trial 2 was to test the hypothesis that coal could be the only supply of the hydrocarbon and sulfur, and produce vapor grown carbon fiber. The pulverized coal was carried into the reactor with a non-hydrocarbon carrier, hydrogen. Upper Freeport Seam coal was obtained from Kaiser Engrs. with 2.5% total sulfur and an estimated 65% carbon content. In this trial designed to run without methane dilution, the molar sulfur/catalyst ratio was 4.5. The formulations are as follows in Table 2. Coal trials A reactor that normally uses a feedstock mixture of 99.9% pure methane was converted to accommodate the use of coal. For catalyst, helium was bubbled through liquid iron pentacarbonyl to provide Fe particles for the 1100 °C reactor. A screw type apparatus was assembled to feed the coal into the injection stream and a carrier gas transported the coal and catalyst into the reactor. Two types of coal trials were made. The first was to test the hypothesis that sulfur-bearing coal can replace H2S as the source of sulfur in the reaction. In this case, coal and methane were used as the hydrocarbon feedstock. Methane was the carrier gas and calculated to maintain a 1.6 molar sulfur/iron ratio. Figure 3. Coal replacing hydrogen sulfide Trial 1 Control and Basic Formulations* Coal This suggests that a fossil fuel such as high sulfur coal may be especially appropriate for consideration since millions of tons of high sulfur coal are no longer being mined due to the 1990 Clean Air Act Amendment. As an example, Ohio coal production has fallen from 55 million tons in 1970 to 33 million tons in 1990 and projected to drop to 17 millions tons. Furthermore, coal would have a tremendous effect on the eventual price of the fiber. The hydrocarbon is the most expensive cost item, followed by the electric oven energy and the catalyst. Although the energy consumption and output capabilities are not yet optimized for a total cost picture, the formulations indicate that the hydrocarbon in coal could potentially cost ten times less than natural gas and totally eliminate the price and hazards of H2S. 10µm Control Trial 1 Methane Coal Sulfur Hydrogen Helium Fe(CO)5 96.90 None 0.47 None 0.96 1.68 87.58 9.33 0.44 None 0.96 1.69 Trial 2 None 80.68 2.02 13.30 1.45 2.55 * Formulations are in percent by weight Results In Trial 1, with coal, methane, and no H2S, the photomicrograph in Figure 3 shows very good growth and confirms that the sulfur contained in the coal plays an active role in the catalytic process, and can potentially replace the need for using H2S in the reaction. The sulfur content in coal is well beyond the optimum amount for the formation of carbon fibers. Nevertheless, this wide range of sulfur acceptability leads to the consideration of high sulfur coal. In spite of its problems for other uses, it may be a unique essential asset for the production of vapor grown carbon fiber. In Trial 2, coal is the only source of both hydrocarbon and sulfur and an SEM photomicrograph is shown in Figure 4. There is good, but shorter fiber formation with a fair amount of soot and/or ash. Nevertheless, these results support the conclusion that the inherent carbon in coal is actively pyrolyzed to products which participate in the catalytic fiber nucleation and growth process. Exhaust Emissions Photomicrographs are the initial estimate of fiber formation. However, X-ray diffraction estimates the graphitic ordering for assuring the quality of the 4 10µm Figure 4. Coal as sole hydrocarbon source Trial 2 fibers strength and conductivity. Table 1 shows that the fiber samples from coal Trials 1 and 2 have a graphitization index that is typical for low modulus commercial fiber. In earlier trials that rely on introducing H2S into a pure methane feedstock at equivalent ratios with the catalyst, periodic analyses were made of the exhaust. To date, sulfur has not been detected in the exhaust. This could be explained by the idea that the sulfur dissolves in such large amounts that it melts the iron catalyst and thus stays with the catalyst at the base of the fiber. How much sulfur can be dissolved as the sulfur increases is unknown. A packed column gas chromatograph (GC) with thermal conductivity detector was used to estimate the composition of the exhaust gases of a series of coal trials when the sulfur was running at 4.5 times the usual amount (Trial 2) and the presence of sulfur was not detected. This instrument does not have the sensitivity to measure nitrogen or sulfur compounds below about 0.1-1 %. Future work is needed with a capillary column GC with dedicated nitrogen and sulfur detectors. Residual Ash There is a wide variation in the organic and ash content in coal. Trials to date indicate that their presence does not inhibit the growth of a carbon fiber. Furthermore, there is no indication that (Continued, page 5) COMMENTARY The Difference Between Informing and Educating Richard Lawson President National Mining Association There is no other nation that surpasses the U.S. in terms of care for the environ- ment, and we can support this by showing nearly $1.3 trillion in expenditures for environmental protection activity since 1980. Tell the miners from me that I shall promote their interests to the utmost of my ability; because their prosperity is the prosperity of the nation, and we shall prove in a very few short years that we are indeed the treasury of the world. These words of Abraham Lincolns were transmitted to a westward-bound Cabinet secretary on the afternoon of April 14, 1865, one of the last official statements made by the president before he left for Fords Theatre. They illustrate the great perceptive insight and depth of understanding that Lincoln brought to so many issues of his time. Undoubtedly, were Lincoln to be magically transported to the modern era, he would not be surprised by the critical position the products of mining have come to occupy in our society. There is no question that mining is inexorably linked, not only in broad terms to our nations prosperity, but specifically to our daily lives as citizens of the United States and the world. This is a great and immeasurable responsibility which every component of our industry - from miner to corporate CEO - takes seriously. At the same time, mining companies also have long recognized another important aspect of their public obligation: that with the right of mineral and coal extraction comes the duty of restoring the land and operating in an environmentally responsible manner. Our most extreme critics would have you believe otherwise. They are quick to demand that the mining industry feel ashamed of its environmental track record. The most severe of these individuals and groups would be satisfied with nothing less than a cessation of mining activity as we know it. Some others, while willing to begrudgingly tolerate limited mining, seek regulations and restrictions so harsh that they border more on the punitive than the practical. Our opponents have attempted to turn these viewpoints into public opinion and, ultimately, public policy. In some instances, as we know all too well, they have succeeded, much to the detriment of our industry and the nation. Yet, we also know from opinion polls that in spite of this, the general public overall does not have a negative view of the mining industry and its environmental performance. In fact, most people do not have an opinion at all, either favorable or unfavorable. What this says, in part, is that we have been doing our job so quietly and efficiently that the average person simply doesnt think about us. But there is also no doubt that we in mining have not done an adequate job of educating - not simply informing - but educating the public-at-large about our unmatched productivity, our environmental performance and minings importance to everyday life, and to the nations security. Providing information and informing people is an action that, in essence, is rather benign. It infers that you are making data available; if your target audience wants to assimilate it, fine. If it doesnt, then it really doesnt matter how good your numbers and arguments are. But education is another process entirely. As the ancient Chinese proverb says, Give a man a fish and you feed him for a day. Teach a man to fish and you feed him for a lifetime. Fundamentally, educating means providing the tools for society to differentiate between fact and fiction and to use information to make intelligent choices. For these and other reasons, effectively educating constituent audiences about mining will be a key activity of the National Mining Association for the foresee(Continued, page 6) 5 the ash becomes embedded in the structure of the fibers during formation and causes inclusion flaws. This type of flaw is intolerable in fiber that is only 0.2µ in diameter. Future Work The next phase will evaluate the sulfur content over a wide range of sulfur/catalyst ratios to establish the highest level that will produce good fiber with no emission problems. In addition, extensive trials will be made to assure that the ash can be consistently removed from the reactor during production without buildup in the reactor. This data will provide the basis for future projections of coal usage. Although residual ash is tolerable for some applications such as rubber or cement, it could be separated from the coal before injection or filtered from the fiber during subsequent pelletization. In practice, the wide range of sulfur and ash in coal will most likely mandate a combination with natural gas to maintain the process balance needed for optimum production. The role of coal has significant implications not only for coal usage, but also could develop a fiber price that would make it possible to consider everyday applications for carbon fiber in rubber, cement and plastic composites. Robert Alig is Senior Research Scientist at Applied Sciences, Inc., responsible for production scale-up of vapor grown carbon fiber. Prior to 1992, he worked on the initial pilot line at General Motors. CAER Goes Global on World Wide Web http://www.caer.uky.edu The CAER has its own home page on the World Wid Web! We have included information on research, upcoming events, information services, and Energeia articles. Come browse with us. If you'd like more information on our Web site, contact Alice Marksberry at 606-257-0308 , e-mail alice@alpha.caer.uky.edu or Kathleen Sauer at 606-257-0288, e-mail sauer@alpha.caer.uky.edu. For question regarding Energeia, call Marybeth McAlister at 606-257-0224, e-mail mcalister@alpha.caer.uky.edu Commentary, (continued) able future. And teaching the truth about our industrys environmental performance will be a key part of the message. What the public will hear is this without question, a fundamental reason the U.S. economy is so competitive is that our mining industry produces products so efficiently, productively, safely and inexpensively. There is no other nation that surpasses the U.S. in terms of care for the environment. And the U.S. mining industry is at the forefront of that great national environmental crusade. This message will be carried in a variety of forums: the Internet, where NMA has its own home page; managing existing educational resources and creating new ones; and taking advantage of traditional media, publication, advertising and communications outlets. Over the long term, our successful use of these avenues to educate will result in a sustainable future, not only for our industry, but also for America and the world. A version of this editorial first appeared in Mining Voice, Volume 1 (5), November/ December 1995. American Carbon Society Workshop Wild Dunes Resort, Isle of Palms, Charleston, South Carolina, USA June 9-12, 1996 The workshop will highlight the diverse ways in which carbon materials are used to prevent and remediate environmental pollution. For more information, please contact: Dr. Fred Baker Charleston Research Center, Westvaco Corporation P.O. Box 118005 Charleston, SC 29423-8005, U.S.A. Telephone: (803) 745-3942; Fax: (803) 745-3742 Energeia is published six times a year by the University of Kentucky's Center for Applied Energy Research (CAER). The publication features aspects of energy resource development and environmentally related topics. Subscriptions are free and may be requested as follows: Marybeth McAlister, Editor of Energeia, CAER, 3572 Iron Works Pike, University of Kentucky, Lexington, KY 40511-8433, (606) 257-0224, FAX: (606)-257-0220, Copyright © 1996, University of Kentucky. UNIVERSITY OF KENTUCKY Center for Applied Energy Research 3572 Iron Works Pike University of Kentucky Lexington, Kentucky 40511-8433 Non-Profit Organization U.S.Postage PAID Lexington, Kentucky Permit No. 51