1 Z D U S T 11 1.4 L A Z D E Z G I N E E R I S G C H E RI I S T 13 Y
.4pril, 1933
40 9
CONCLUSIOXS By calculating the value of awas Schule has done ( I 6 ) , all the constituents of the flame are considered to be in equilibrium with the atmosphere, b becomes zero, and ( Y & is 0.1195. For practical purposes this assumption is correct, since the flame issued from the torch at 0.4 inch (10.2 mm.) of water pressure above atmospheric. The volumes of the gaseous constituents in the flame then are:
+
0.564)](1 - O I H ) = 0.5033 X 0.9398 0.564(1 - CY,) = 0.564 X 0.8805 2a.q X 0.5033 = 0.1204 X 0.5033 '/.(Y, X 0.564 = 0.0598 X 0.564 [0.436
Hg:
H20: H,: 0 9 :
(aw X
Total volume
70of
O2 in flame
=
(y::::;) ~
These results show what temperatures may be realized with many of the common gaseous fuels and the narrow range of adjustment permissible a t peak temperatures. The practical application of these oxygen-gas mixtures lies essentially in the field of welding, since the cost of oxygen is still too great for the large quantities demanded in furnace work. Besides, cheap refractories that will withstand these temperatures are not available. IJTERATURE CITED
0.473 cu. = 0.497 cu. = 0.0606 cu. = 0.0337 cu. =
=
m.
m. m.
m.
1.0643 cu. m.
100 = 3.16
Taking the heats of dissociation of hydrogen and water
at 3000" K. and one atmosphere pressure as 4020 and 2510 calories per cubic meter, respectively, and using the heat contents of the gases from the tables prepared by Schule (18), a temperature of 2955" K. (2682" C.) is obtained. From the oxy-hydrogen temperature curve calculated by Felbeck (4),a valueof 5255" F. abs. (2902" K.) is obtained at the ratio of gases used in the preceding calculation. This value is in close agreement to that measured (5310" F. abs.), although the percentage of oxygen liberated in the flame by the dissociation of water seems to be rather low. His value is probably too low since the present authors obtained a measured temperature of 5310" and a calculated one of 5350" F. ab&.
Bunte, K., Gas- u . Wasserfach, 74, 712 (1931). C h a p m a n , W.R., J . C'hern. Soc., 119,1677-53 (1921). FBry, C., C'ompt. rend., 137,909-13 (1903). lbeck, G. F., Univ. Ill. E n g . Expt.
I h i d . , p. 92. I h i d . , p. 106. I h i d . , pp. 137, 119. Henning, F., a n d Tingwaldt, C., 2. Phuaik, 48, 805 (1928). Jones, G . IT., Lewis, B., Friauf, J. B., a n d Perrott, G. S t . J., J . Am. Chem. Soc., 53,869 (1931). Joos, H., Autogene Meta!Zbearbeit,, 24, 211, 239 (1931). Kurlbaum. 2. Physik, 3,187,332 (1902). Lewis a n d Randall, "Thermodynamics," p. SO, McGraw-Hill, 1923. Loomis, A . G., a n d Perrott, G. Yt. j,,ISD. EKG.CHEJI.,20, 100-i (1928). P o t h m a n n , A utogcne Metallbearbeit., 20, S o s . 4 and 5 (1927). Schule, IT., "Neue Tabellen und Diagramme fiir technische Feuergase," pp. 42-53, Springer, 1929. I b i d . , diagram p. 60. I b i d . , pp. 102-6. Ibid., tables pp. 113-13. Whittemore, H., L-nir. Ill. Eng. Expt. St,a., B I L L45, 5b (1910). R E C E I V ESeptember D 2 6 . 1932. Washington Blvd., Chicago, Ill.
H. H . Lurie's present address is 4153
Hydrogenation of American Coals in Anthracene JV. L. BEUSCHLEIN AND C. C. WRIGHT Department of Chemical Engineering, University of Washington, Seattle, Wash.
T
HE hydrogenation of some -4mericaii coals was reported
recently by the authors ( 2 ) . I n this work, phenol was used as the dispersion medium, and the degree of hydrogeiiation of the coals, which ranged in rank from low grade bub-bituminous t o semi-bituminous, was expressed in terms of the relative conversion of each coal into phenol-soluble products. Csing the same coals, but with a procedure comparable to that of commercial practice, the present investigation forms a basis of comparison betn-een the results from thme theoretical investigations and those from the industrial process. Sumerous patents have been granted covering the various phases of the commercial hydrogenation of coal and subsequent separation of products. I n general, however, the es.;entia1 features of the processes are very similar Coal admixed with some suitable dispersion medium, surh as heavy benzene, naphtha, or mineral oil, is treated with hydrogen under high pressure a t temperatures of about 450" C. The products, after remora1 of the water, are leached or extracted with gas oil, or benzene, and the extracted residue is either returned for further hydrogenation or carbonized to yield a liquid distillate and coke. For experimental investigations on a laboratory scale, the use of the customary dispersion agents preqents tn-0 un-
desirable features-namely, the hydrogenation of the dibpersion medium and the separation of the medium from the products. Inasmuch as heavy benzene might be considered a light oil highly charged with anthracene, recent inveqtigations by Gillet ( 3 ) on the solution of coal in anthracene oil, together with those of Kling and Florentin (4) showing tlle stability of anthracene toward hydrogenation, suggest thii solvent as a suitable medium. The present report, therefore, describes experiments in which the dispersion agent n aanthracene. Previous studies ( I ) on American coals and a phenol iiiedium had shown that ninximum conversions were obtained a t a hydrogen pressure of 211 kg. per sq. cm. and a t a temperature of 350" C. For comparative purposes these conditionwere maintained throughout the present work.
EXPERIMESTAL METHOD A mixture of finely divided coal and anthracene in the ratio of 2 to 1 was hydrogenated under constant volume conditions a t 350" C. for a period of 8 hours. The initial hydrogen pressure a t room temperature was 141 kg. per sq. em. The products were extracted with benzene in a Soxhlet apparatuq, and the insoluble reqidue was subsequently carbonized a t
410
I N D U S TR I A L A N D E N G I N E E R I N G C H E M I S TR
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Vol. 25, No. 4
550" C. in a Fischer retort. I n a second series of experiments, nitrogen was substituted for the hydrogen, and the same procedure was followed.
nitrogen runs are, in general, approximately twice as great as those from the respective experiments wherein hydrogen was used. These results indicate that the process of hydrogenation involves the conversion, into benzene-soluble prodDISCUSSION OF RESULTS ucts, of those constituents of the coal which normally yield The physical effect of the hydrogen t.reatment, was readily the gas and liquor fractions upon low-temperature carbonizaapparent. After hydrogenation the charge was brittle and tion. No simple correlation between the conversion and any of pitchlike in appearance and broke with a shiny fracture. After the bomb and contents had cooled to room temperature, the common methods of coal classification was evidenced by a relatively large decrease in pressure was always found to plotting the first factor against percentages of carbon, fixed have taken place. Invariably a quantity of water and light carbon, or ratios of carbon to hydrogen, carbon to net hydrooil collected a t the bottom of the bomb, the heavy oils and gen, etc. The coals showing the most satisfactory conversolids remaining in the steel thimble provided for them. I n sions were those of the sub-bituminous and low-grade bitumicomparison, the nitrogen treatments caused no apparent nous classes. These results are in contradistinction to those physical change beyond a slight caking, probably because of obtained in phenol experiments (8), where good correlation cementation caused by crystallization of the anthracene upon was shown between percentage carbon and percentage concooling. After room t,emperature had been attained by the versions, and where maximum conversions (based on perbomb and contents, a slight increase in gas pressure was not.ed. centage of phenol-insoluble residue) were obtained for coals No oil collected on the walls of the bomb, and water was found of the high-ranking bituminous and semi-bituminous classes. only in those experiments where the coals used were of low Furthermore, comparisons between the yields of total tars reported for this series of experiments and those of C prodrank. ucts (phenol- and chloroform-soluble portions) or B and C TABLE I. DISTILLATION OF HYDROGENATED COALS~ products (total phenol-soluble portions) previously reported P R O D U C T S FROM (Z), show virtually no correlation. These results lead to the GAS LOW-TEMP. conclusion either that the conversion of coal by hydrogenation TREAT- CARBONIZATION TOTAL COAL^ MENTC Coke Gas Liquor TAR COXVERSION is a function of the solvent or that the methods used for de% % % % % termining and reporting conversions for the phenol experiFairfax, Wash. N 83.0 4.5 5.4 H 72.5 3 . 2 3 . 7 13.6 ments give little if any basis for estimating the commercial 6 . 6 3 . 1 10.1 N 80.9 Wilkeson, Wash. adaptability of the various coals for the hydrogenation H 59.8 5.3 2.2 23.2 Flat Top, Ala. N 81.4 6.6 5.1 process. H 55.1 3.5 3.5
Ocean 2, Pa.
Boone 2, W. Va. 204, Ky.
N H N H
78.5 47.7 77.0 64.8 78.0 58.6 73.0 42.5 84.1 56.0 70.0 47.6 71.8 55.5 70.8 42.9 73.2 38.0 72.2 32.6 66.0 33.0
6.8 2.6 6.4 3.4 8.3 3.7 6.3 2.9 6.5 3.7 11.2 2.9 7.5 3.5 5.3 2.9 8.6 1.4 6.6 1.9 7 6 115
5.5 2.5 5.5 3.2 6.7 2.9 5.4 3.4 5.9 2.8 4.9 2.9 6.2 2.4 5.7 3.8 5.'7 2.2 3.8 2.1 5.0 2.5
N 9.2 H 23.8 l9 N 8.71 H 35.2 31 11.7 N Orient 1, Ill. H 27.5 7.3 Occidental, Wash. N H 28.3 8.8 Rolapp, Utah N H 19.8 6.2 Roslyn 7 , Wash. N 26.8 28 H NewBlackDirtmond, Wash. N 5.71 35 H 28.8 Tono, Wash. N 7.5 H 42.5) 40 N Ford's Prairie, Wash. H 3:::] 33 a All results reported on ash- and moisture-free basis. b A complete description of the coals has been presented in a previous paper ( 8 ) . c Results designated by N and H are those obtained with nitrogen and hydrogen, respectively.
Roslyn 3, Wash.
I n Table I are presented the data for the hydrogen and nitrogen experiments conducted on the fourteen coals investigated. For the purpose of comparing present and previous work, the percentage conversion of R coal has been calculated as the difference between the percentage of coke produced in the nitrogen and in the hydrogen experiments. The percentage of total tars reported includes all liquids, after removal of water, resulting from the extraction and carbonization of the nit,rogen-treated or hydrogen-treated coal. The yields of gas and liquor resulting from the low-temperature carbonization of the extracted residues from the
EXPORTS OF PETROLEUM INCREASE. Exports of United States etroleum during January revealed a rise of 22 per cent over becember's figures, according to the Department of Commerce. Total shipments for January amounted to 7,999,000 barrels valued at $15,667,000, compared with 6,574,000 barrels, valued a t $13,622,000 for December, 1932, and 8,445,000 barrels valued at $17,685,000 for January, 1932. January's exports were only 5 per cent less than the corresponding month in 1932. Imports during January amounted t o 3,993,000 barrels, com-
SUMMARY Experimental data have been presented for the hydrogenation of a series of American coals wherein anthracene was used as the dispersion agent. Nitrogen experiments under like conditions formed a basis upon which to estimate conversions. For the coals investigated, maximum conversions were obtained for coals of the low-ranking bituminous and sub-bituminous classes. No definite correlation was found between the degree of conversion and the classification of the coal. A definite lack of correlation was shown between the conversions determined by methods essentially similar to those used in commercial practice, and those based upon the conversion into phenol-insoluble residues.
ACKNOWLEDGMENT The authors are indebted to the United States Bureau of Mines from which the samples of coal were obtained. The investigation was made possible by a Grant-in-Aid of the Kational Research Council to W. L. Beuschlein. LITERATURE CITED (1) Beuschlein, W. L., Christensen, B. E., and Wright, C. C., IND. EXG.CHEM.,24, 747 (1932). (2) Beuschlein, TV. L., and Wright, C. C., Ibid., 24, 1010 (1932). (3) Gillet, A,, Proc. 3rd Intern. Conf. Bituminous Coal, 2, 1 (1931). (4) Kling, A,, and Florentin, D., Ibid., 2nd. Conf.,2, 523 (1928).
RECEIVED October 3, 1932.
pared with 3,984,000 barrels for December, 1932, and 5,683,000 barrels for January, 1932. Imports during January were only two-tenths of one per cent higher than in December. While the total value of exports in January was greater than in December, it was pointed out that the average value per barrel declined from $2.07 in December t o $1.96 in January. Gasoline exports advanced 23 per cent in volume to 2,250,000 barrels; gas and fuel oil advanced 67 per cent to 1,994,000 barrels; and kerosene advanced 38 per cent t o 872,000 barrels.
