INDUSTRIAL AND ENG INEERING CHEMISTRY
November 1951
2581
CONTENTS OF ASPHALTICCONSTITUENTS VI, NITROGEN TABLEV. PER CENT QF NITROGENPRESENT IN RESIDUUM TABLE FROM OREQON BASIN, WYO., A N D MEXICAN ASPHALTS Nitro en in Nitrogen, Weight %
Petroleum
0.06 0.11 0.12 0.58 0.27 0.16 0.08 0.28 0.25 0.22 0.17 0.23
c i o m o -c010. Dallaa b y o . Derby( Wyo. Pilot hutte wyo. Keri Greeo’e Ciroie Ridge, WYO.
Nitro en in Re&urn Weight %’ 0.16
Residluum Wei h t % 6f Total%trogen
Nitrogen, Weight % Oregon Basin Tampioo 0.35 0.64 0.13 0.88
88.3
106.0
0.24 0.32 1.15 0.60 0.34 0.20 0.54 0.53 0.52 0.26 0.50
90.8 84.5 88.9 87.5
1.18
0.50 0.05 0.78 1.06
100.0
96.4 96.0 95.4 94.1 95.7
(2) Hubbard, R. L., and Stanfield, K. E., Anal. Chen,, 20, 460 (1948). (3)Hughes, E,,and Blade, 0. C., U. 9. Bur. Mines, Inform. Cite. 7470 (1948). TABLEVII. EQUATION CONSTANTS FOR CURVESRELATINQ (4) Lake, G.R.,McCutchari, Philip, Van Meter, Robin, and Neel, CONTENT CARBON RESIDUEAND NITROGEN J. C.,Anal. C h m . , in press. Elope, (5) McKinney, C. M,, and Blade, 0. C., U. S. Bur. Mines, Rep/. Intercept, 7 Nitro enL‘ Invest. 4289 (1948). Geological Period % Nitrogen % barbon b d u e (6) Mapstone, G. E., Petroleum Reline?, 28, 111 (1949). 0.030 f0.019 Carboniferous (7) Maxted, E. B., J . 500.Chem. I d . (London), 67,93 (1948). 0.011 f0.015 Cretaceous 0.019 fO.019 Devonian (8) Mills, G.A., Boedeker, E. R., and Oblad, A. G., J. Am. Chem. 0,012 fO.006 Juraasia SOC.,72, 1554-60 (1950). -0.019 0.068 Ordoviaian (9) Poth, E. J., Armstrong. W. D., Cogburn, C. C., and Bailey, 4-0 016 0.066 Tertiary J. R.. IND. ENC~. CKEM.. 20,83 (1928). (10) U. S. Bur. Mines, Repl. TABLEVIII. AVERAQEDEVIATIONS 1N CALCULATION OB NITROQEN CONTENT Inuest. 4652, 63 (1950): 4457, 49-50 (1049). Average Deviation, Samples Having Nitrogen Contentd Average (11) Univeraal Oil Products Co., 0.3 to 0.5 and No. of Geological Eamplas Period 54 Carboniferous 25 Cretaceous Devonian 4 Juraasic 4 Ordovician 6 41 Tertiary All 134
-
Up to
Deviation All Samplh 0.032 0.011 0.020 0.013 0.019 0.069
0.099 0.026 0.018 0.021 0.013 0.015 0.044
o.oas
0.027
0.1 to 0.19 0.027 0.012 0.018
0.2 to 0.29 0.036
0.49 0.108
Method A-120-40, Chi-
cago. 1947.
0.035 0 044
0 1086
0.103
0.141
0 * 028
0.046
0.104
0.141
I
“U.O.P. Laborstory Test Methods for Petroleum and Its Products,”
over
RIDCEIVED Ootober 3, 1950. Pra sented before the Division of Gas and Fuel Chemistry a t the 118th Meeting of the AMERICAN CEIEMICAL ~ O C I E T Y ,Chicago, Ill.
residue were exhibited but these were not 80 close to straightline relationships and more exceptions were apparent. DISCUSSION
The use of nitrogen content
EM a
means of identifying source
beds in which petroleum originated seems to show aome promise. The ratio of per cent nitrogen to per cent carbon residue appears to be an indication of the geological origin. These ratios lor petroleum from various geologkal periods are Tertiary, 0.066; Cretaceous, 0.011; Jurassic, 0.012; Carboniferous, 0.030; Ordovician, 0.068; and Devonian, 0.019. The naturally occurring bitumens correspond somewhat to these ratios, the three of Tertiary origin having ratios of 0.076, 0.070, and 0.078, while that from the Cretaceous haa a ratio of 0.032. The Rhale oils give vnlues for the ratio ranging from 0.102 to 1.047, dofinitely indicating their different character. Sulfur content fnils to show aa close a relationship with nitrogen content as carbon residue. This may be brcnusc! it is derived from two sources-organic starting material und reduction of inorganic eulfstes. Nitrogen, on the other hand, is derived chiefly from the organic source material. ACKNOWLEDGMENT
Most of the samples of crude oil were made available through H. M. Smith, Bureau of Mines, Bartlesville, Okla. The samplea of asphaltic oils, resins, and asphaltones were contributed by K. E. Stanfield and R. L. Hubbard of this station. LITERATURE CITED
(1) American Society for Testing Materials, ASTM Designation D 189-46, “ASTM Book of Standards,“ part 5, p. 801, 1949.
Corrections In the artidle on “Equilibrium Flash Vaporization of Petroleum Crude Oils or Fractions” (Othmer, D. F., Ten Eyck; E. H., and Tolin, Stanley, IND.ENQ.CHEM.,43, 1607 (1951)] the titles of Figures 3 and 4 have been transposed.
Figure 6
In the article on i‘Thermodynamic Correlation of Vapor-Liquid Equilibria [Gilmont, Roger, Weinman, E. A,, Kramer, Franklin, Miller, Eugene, Hashmall, Frank, and Othmer, D. F., IND.ENQ. CHEM.,42, 120 (1950)] Figure 6 should be for the system benzene-ethylene chloride instead of benzene-carbon tetrachloride. The correct figure is given here. D. F. OTHMER ROGER GILMONT
