Solid and Gaseous Fuels R. F. Abernethy
and 1. G. Walters, Bureau of Mines, U. S. Department of Inferior, Piffsburgh, Pa.
T
of a series of reviews on methods of sampling, analyzing, and testing solid mineral and gaseous hydrocarbon fuels. The period covered by this review is October 1964 to September 1966, inclusive, and it follows the general format of previous reviews. HIS IS THE TEXTH
SOLID MINERAL FUELS
This section is concerned with studies on methods of sampling, analyzing, testing, and evaluating coal, coke, and related materials. Most of the investigations reported are related to present standard methods and are proposed for the purpose of improving the accuracy or reducing the time of analysis. In the miscellaneous tests section are items of related interest to solid fuel technologists. Sampling. The proposed I S 0 specification for coal sampling was tested by two trials by Crawford and Smith @A). Sampling was done a t stages between mine and power station; also included was coal transported by sea and rail. Keller (4A) made tests to determine the variance of sample preparation and the quantities of sample required for testing. A scheme for the determination of precision for various steps in sampling, sample preparation, and analysis was presented by Aresco and Orning ( I A ) . The variances for each step are treated as a function of preparation, top size as sampled, and ash content. Sporbeck (8A) describes certain errors that are possible in sampling and indicates acceptable equipment. He introduces some novel instrumen ts . Tibbetts, Featherby, and Miller (9A) prepared guidelines for the design, selection, cost of installation, and justification for installing automatic coal-sampling devices. I n the analysis of coke the quantity of sample required depends on the specific test. Sorkin, Pedan, and Sulimova (7A) determined the minimum weight for each test. The validity of the weights of sample selected is based on the comparison of analyses made on individual pieces of coke with those from automatically collected samples per shift. The preparation of the sample after collection is of equal importance. Riley (5A) discussed the Bond theory and described coarse crushing, intermediate crushing, and fine grinding. 248 R
ANALYTICAL CHEMISTRY
Vibration grinding mills have certain advantages over ball mills, according to Smith (6A). A new type of mill for crushing and reducing the quantity of sample, described by Zbraniborski (IOA), consists of two vertical cylinders separated by a sieve. The upper cylinder has a rotary breaker and the lower one has a device to direct the crushed coal to the sides of the container. Usually there are varying times of delay between the preparation of the laboratory sample and the analysis. DeSieghardt and Cole (3A) compared effects of air, nitrogen, and water on the storage of the laboratory sample. Proximate Analysis. MOISTURE. Bull (5B, 6 B ) stated that the British Standards min;mum-space oven for the weight loss method for moisture in brown coal was not satisfactory. Certain modifications in procedure would be required to make it acceptable. The advantages and limitations of the British Standards Method 1016 for moisture in brown coal are discussed by Evans (9B). Mchlillan (R8B) reports that the I S 0 procedure for moisture in b r o m coals and lignites is by distillation with xylene or toluene and not by weight loss on heating. The moisture in various grades of coal and coke can be determined by nuclear magnetic resonance according t o Ladner (85B). The interferences due to mineral matter and particle size are described by Ladner and Q7heatley (26B). Continuous measurements of moisture in coal and coke with variations in application are described by Kobayashi (19B),Dresia and Fischotter (8B), Schuricht (37B), and Stewart and Hall (41B ). The measurement of moisture in coking coals by the dielectric constant method is described by Hornig (I5B). Its application to broivn coal in a briquetting plant is discussed by Kersting (17B). Wilkinson's (42%) recent work on the moisture in the laboratory sample of coke showed that the 100' to 110' temperature should be raised to 300'. Rapid or control methods for moisture have been studied by Xemec and Kas (3bB). They compared methods based on hot air, infrared, and the reaction of moisture and calcium carbide. Ruschev and Tomova (35B) compared heating methods, infrared, xylene distillation, rise in temperature on addition
of HzS04, DTA, and conductance measurements. Lorant and Pollak (27B) modified the acetyl chloride method for moisture in coal and obtained satisfactory results. VOLATILE MATTER. The composition of the volatile matter of coke was determined by Bertling and Echterhoff (2%). A thermobalance was used a t 880'. They found that the volatile matter evolved was related to the particle size of the sample. Occluded gases and moisture were released a t 100' to 200' and the gases a t 600' to 700" consisted of decomposition products of compounds formed by oxidation of coke. Knauf (18B) found that the volatile matter of coke consisted of thermally unstable products of carbonization, products of decomposition of oxidation of compounds, and occluded Tu' and Con. Experiments by Peters and Bertling (34B) show the effect of rapid devolatilieation of coals. The yield of volatile matter is higher a t the more rapid rates of heating. There is less gas but much more tar and pitch produced a t the rapid rate of heating. Greenfield and Smith (12B)developed a method of consecutively determining volatile matter, fixed carbon, and ash in anthracite. The sample is heated a t 925' in a N atmosphere. The volatile matter is passed over Co(I1)Co(II1) oxide heated to 625', the resulting COz was absorbed in KOH and determined by change in conductance. The N in the combustion tube was changed to purified 0 to convert the fixed carbon into Cot. It was determined quantitatively as for the volatile matter. The residue or ash remaining was weighed. The effect of the interaction of siderite with the coal during the volatile matter determination was studied by Bardhan and Gupta ( I B ) . Corrections were developed to adjust for errors in the analysis of washery products. ASH. The rapid method of ashing coal was modified by Kozko and Ryukina (83B). Forced air circulation over the samples reduced the time of test considerably. Kudela and Kedronova (d4B) further improved Pozetto's rapid method of ash determination of coal by discontinuing heating as soon as the glowing of carbon ceases. Tolerances for various ash contents are proposed: up to 307, ash, 0.27,; 30 to 4oy0 ash,0.3%; and t. 6677 (lo), 28 (1965). (12G 1 English, P., IIioriis, F. J., I K M 7’runs. 75 (713), CSi-CE14 (March 1966). (13G) Gebert, F., Kodin. H., Steiner. H., Brennstoff-C’henz. &, 225-8 (August 1964). (14C;) €Iinz, H., Ibid., 46 ( 7 ) , 200-3 i1965). (15G) Iloy, A., llaehre, K., Ibid., 47 (2), 59-60 (1966).
(1bG) Jellinek, V,,Paliva 42, 214-15 (1962)
(1iG) Kessler, 11. F., Dockalova, L., Brennstofl-Chern 46 (61, 172-5 (1965). (18G) Kirsch, H., Tech. 1 ‘eberwach. 6 (6), 20\Insart, J., Fonderze belge 34, 225-9 (1964). (23G) ll.tyland, H., Fu.2 45 ( l ) , 97-8 (1966).
Reviews
(35) Belousov, T’. &I., Gershingorina, A. 1 ., Ukr. Khirn. Z h . 31, 633-5 (1965). (4J)Berezkin. V. G., Mvsak. A. E.. Polak, L. S., Gaz Khromatogr., A k & S a u k SSSR, T r . Vtoroz Vses. Konf. MOSCOW, 1964 332-4. (55) Blakemore, G., Hillman, G. E., Analyst 90, 703-14 (1965). (6J) Bombaugh, K. J., Hayes, B. J., Shaw, W. R., J . Gas Chromatog. 3, 373-7 (1966). ( 7 5 ) Breshchenko, T.-. Ya., Ivanova, L. \ ., Rabinovich, S. I , “Veftepererabotka i .\‘eftekhzm., Sauchn.-Tekhn. Sb., 1965 37-8. (8J) Bruk, A. I., Tinogradova, L. >I., Yzakhiren, D. A., Gaz Khromatogr, A k a d . 4 a u k SSSR, T r . Vtoroz Vses Konf. NOSCOW, 1964 119-24. (9J) Cerronf, ll.,Piatti, U.,Chzrn. I n d . 46, 1054-63 (1964). (1OJ) Eckert, F., Gas-lt’asserfach 106, 538-40 (1965). (11J) Goinak, A. I., USSR Patent 164,581 (1964). (125) Gornak, A. I., Ermolenku, S . F., Dokl Ahad. X a u k Belorussk, SSSR 8, 795-8 (1964). (135) Habgood, H. K., Can. J . Chrnc. 42, 2340-50 i 1964). (145) Harris, W.’E., Habuood. IT. 1V. -.T.Gas Chromatog. 4. -, 1’ -*4-i7 (1666). (155) Hoffmann, R. L., List, G . R., Evans, C. D., -Vatwe 206, 823-4 i 1 (16.5). .16J) Jacobs, E. S., ANAL. CHEM.38, 43-8 11966). ( l 7 J ) Kavan, I., Prace C‘staLu V y z k u m Palzv 7, 246-56 (1064). (185) Ihtd., 11, 204-17 (1965). (195) Kiselev, A. I-.)Chernen’kova, Yu. L., Yashin, Ya. I., .Veffekhzmiya 5, 141-8 (1965). (205) Knipschild, J., Pagnier, G., Brennslo$-Chenc. 44, 8-10 ( 1 9 6 3 ) . (215) Knotorovich, L. >I., Bovrova, V. P., Gar Khromatogr., Akad. ,Yauk SSSR, Tr. Vtoroi Vses. Konf., Jloscow, 1964 119-24. (225) Kraplina, Kh. F., Krichmar, S. I., Pinsker, A. E., Koks z Kham. 1966 12). 43-6. (235)’ Lambert, Charles (to Air Liquide), French Patent 407,759 (1965). (245) Leggoe, J. H., Hoffman, N. L., Kahn, F.. Brewer. J. E.. U.S. Patent 3.206:968‘11965). ’ (25J) LLyd, It. J., Ibid., 164,980 (1965). (265) Ibid., 212,322 (1965). (27J) Lueth, E., Arch. Ei.senhueftenu8. 35, 1151-60 (1964). (28J) Lulova, N. I., Tarasov, A. I., Kuz’mina, A. V., Fedohova, -4. K., Leont’eva, S. A., Gaz. Krornatogr., .Ikad. >Yauk SSSR, T r . T’toroL Vses. k‘onf., Afoscow, 1964, 162-72. (295) Lysyj, I., Newton, P. H.,AXAL. CHEV. 36, 949-50 (1964). (305) llarvillet, L., Tranchant, >I., Methodes Phys. Anal. 1965 37-9. (315) X y a k e , H., Llituoka, >l.,-Vzppon Kagaku Zasshz 85, 326-31 (1964). (325) Sikolaeva, J7. T r . C-jLmsk. .\-eft. Sauchn.-Issled. Inst. 1964 (13), 243-52. (335) Roberts, A. L., Ward, C. P., Inst. Gas Engrs. J . 5, 313-25 (1965). (345) Sharma, R. K., llcLean, L). IIProceedings ., of Xational Analytical Instrument Symposium, pp. 307-25, 1964. (4U) Larson, C. A., U. S. At. Energy Comm. RFP-564 i1965). (5U) Spaggiari, ?VI: A.,’ Turtura, L., Ria. Combust. 18, 267-79 (1964). (6U) S’lckova, Z., Base, J., Prace Ustavu Vyzkum Paliv 11, 218-29 (1965).
