INDUSTRIAL A N D ENGINEER1 NG CHEMISTRY
February, 1924
*
ACKNOWLEDGMENT Acknowledgment is made to L. W. Nichols, J. H. Carter, and Miss M. Black, of the laboratory staff of the Atlantic Refining Company, who made most of the determinations and gave many valuable suggestions during the work. BIBLIOGRAPHY '
1---Donnan, Z . physik. Chem., 31, 42 (1899). 2--Stanton, Archbutt, and Southcombe, Engineering, 108, 758 (1918). 3---Herschel and Anderson, Bur. Standards, Tech. PaDer 223 (1922).
135
4-Morgan, J . A m . Chem. Soc., 33, 658 (1911). 5-Harkins and Brown, Ibid., 41, 499 (1919). 6-Harkins and Brown, Ibid., 98, 246 (1916); Harkins and Humphrey, I b i d . , 38, 228 (1916); Karkins and Cheng, Ibid., 43, 35 (1921); Harkins, Brown, and Davies, Ibid., 39, 354 (1917); Harkins, Davies, andClark, Ibid., 39, 641 (1917). 7-Quincke, Pogg. A n n . , 139, 126 (1870); Antonow, J . ckim. Bhys., 5, 372 (1907); Lewis, Phil. Mag., [61 16, 499 (1908). 8-Gurwitsch, Petroleum Z.,18, 1269 (1922). 9-Bartoli and Stracciati, A n n . chim. phys., 7, 382 (1866); Rittman and Egloff, J . I n d . Eng. Chem., 1, 578 (1915); Francis and Bennett, I b i d . , 14, 627 (1922). I b J a g e r , A k a d . W i s s . m i e n , 100, 2A, 493 (1891).
Some Characteristics of t h e Hydrocarbons in Midcontinent Kerosene' By C. R. Wagner LION OIL REFININGCo., EL DORADO, ARE.
naphtha. This oil gave the T IS a well-recognized A closely fractionated lprosene cut from Midcontinent (ohlafOrmOlite6reaction for arofact that Midcontinent homa) crude was separated into two fractions by use of liquid matic compounds and was (Oklahoma) crude, even sulfur dioxide. The insoluble portion gave eoidence of CnH2, readily attacked by nitric in the lower boiling point hydrocarbons; but no hydrocarbons of the parafin series. The and sulfuric acids. fraCtiOlls, gives a product oils soluble in sulfur dioxide, from their specific gravity, index Before going further with which is very differentfrom of refraction, carbon-hydrogen ratio, and boiling points, belong the work, qualitative tests Products of the same boilto the hydrogenated naphthalene series. ing points produced from were made on two other Pennsylvania crude. The fractions, one of specific automobile tourist who measures the value of gasoline solely by gravity 0.7927 (47.0 Be.) and with a boiling point range of 146" its Baume gravity2 can never be convinced that 58.0 gravity to 210' C., the other of specific gravity 0.8132 (42.5 Be.) and gasoline at St. Louis may have as good a distillation range as with a boiling point range of 192' to 240" C. With great sur62.0 gravity gasoline a t Bradford, Pa.2 It is also very com- prise it was found that the quantity of SOrsoluble constituents monly said that this difference in gravity is due to an admix- increased roughly in proportion to the increase in specific ture of naphthene (cyclohexane) derivatives with paraffin gravity and average boiling point. The specific gravity of these SOz-soluble fractions also increased with the rise in hydrocarbons in the Oklahoma crude. It was thought worth while to make some tests to ascer- boilihg point. Because of the larger proportion of the S O r tain, if possible, the character of the hydrocarbons present solub€e compounds in the heavier cuts and because of the in the Oklahoma crude. It had been frequently noted that greater ease of securing a closely fractioned oil in considerable it was very difficult by ordinary methods to secure a product quantities, it was decided to carry on the investigation with which would be unattacked by 66" Be. sulfuric acid (93.19 this heavy fraction. Several treatments of 1-liter quantities gave percentages per cent HzSO4). This fact suggested the presence of aromatic compounds. Attempts to freeze out paraffin hydro- of SOz-soluble oil ranging from 4.6 to 6.0, with an average of carbonri from heavy gasoline and kerosene fractions were 5.4 per cent. The procedure followed was to agitate the fruitless, even a t temperatures as low as -50" C . , causing oil vigorously with one-third its volume of liquid sulfur diconsiderable doubt as to the presence of compounds of this oxide a t -10" c. or lower. After allowing to settle, the series in any but the lightest fraction of the petroleum. lower layer was removed and a second treatment made in The method of Moore, Morrell, and Egloff3 for separating the exactly the same manner as the first. Sometimes a third constituents of a special naphtha of specific gravity 0.7527 treatment was made when the second yielded an appreciable (56.5 Be.) was tried. This naphtha, as well as all other oils quantity of soluble oil. After evaporating off the' sulfur investigated, was made by topping methods, which insure dioxide both the soluble oil and the insoluble oil were washed the presence only of compounds originally present in the with large quantities of cold water, neutralized with strong caustic, and again washed with water. I n every case it crude oil. It had a boiling point range4 of 100" to 160' c. One thousand cubic centimeters were treated a t -10' c. was found that the boiling points of the two fractions were with liquid sulfur dioxide (in the ratio 2 parts oil t o 1 part unchanged. The specific gravity of the insoluble oil ranged sulfur dioxide) and the sulfur dioxide was evaporated from from 0.8100 (43.2 Be.) to 0.8081 (43.6 Be.) and the specific the lower layer. After neutralizing with sodium hydroxide gravity of the soluble oil from 0.9159 (23.0 Be.) to 0.9094 and washing with water about 30 cc. of a slightly fluorescent (24.1 Be.). oil were obtained, which had a specific gravity of 0,8388 Where the sulfur in the original oil had been 0.046 per cent, (37.2 Be.) and the same boiling point range as the original the insoluble oil now contained 0.016 per cent, and the soluble oil 0.54 per cent. This soluble oil nitrated very readily with Presented before the Division of Petroleum Chemistry a t the 66th dilute nitric acid at the temperature of the bath, formMeeting of the American Chemical Society, Milwaukee, Wis , September 10 t o 14, 1923. ing a red viscous liquid, which resisted all attempts to crystalZAiI gravities given in this paper, B a u d or specific, were taken a t lize it. The product formed by action of concentrated 16.6*/15.6" C. nitric acid alone or in the presence of concentrated sulfuric * Chem. Met. E n g . , 18, 396 (1918).
I
f
Bur. M i n e s , Tech. Pa$er 214.
6
Holde, "Examination of Hydrocarbon Oils," p. 38.
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
136
Fraction I
I1 I11 IV
Vol. 16, No. 2
TABLE I-ANALYSIS O F SOZ-SOLUBLE E'RACTIONS FROM MIDCONTINENT CRUDE Distillation Range Molecular Formula at 5 M m . Specific Gravity H Weight Suggested C S 71 to 82 0.8697 1.4925 88.71 11.15 0.045 168 C1:His 82to 93 0.8866 89.19 10.99 173 0.021 Cl4HlO 93 to 104 89.56 0.9117 1.5238 10.30 0.054 167 CiaHis 104 to 115 0.9383 1.5448 90.27 0.062 9.49 177 CirHis
.? ....
Calculated Analysis C H 88.88 11.12 89.36 10.64 89.66 10.34 90.32 9.68
TABLE 11-ANALYSIS OF Sol-INSOLUBLE FRACTIONS FROX MIDCONTINENT CRUDS Fraction
I I1 111 IV V
VI
Distillation Range at 5 M m . 71 to 82 82 to 83 83 to 88 88 to 93 93 to 95 95 to 103
Specific Gravity 0.8100 0.8109 0.8118 0.8123 0.8125 0.8120
ny
....
.... ....
1.4500
....
1.4517
C
H
S
8k:f3 85.38 85.27 84.86 85.46
l3:il 14.09 13.85 14.35 14.21
0.011 0.012 0.013 0.010
was essentially the same, but the reaction with concentrated nitric acid proceeded with explosive violence. It could only be controlled by keeping both acid and oil cooled by ice and salt and adding the acid very slowly. It was thought that the presence of these sulfur compounds might be the cause of this violent reaction, and attempts were made to remove them by fractional distillation, by distilling with mercury, mercuric oxide, copper oxide, metallic sodium, and lead oxide. Finally, fuming sulfuric acid was used, but none of these methods materially reduced the sulfur content. Several gallons of a specially processed low-sulfur oil were prepared in the hope that the SOz-solublefraction would be correspondingly low in sulfur. No attempt was made to determine the quantity of SOrsoluble oil in the sample, because the treatment which it had received made it certain that some of these fractions had been removed. When it was found that the SOrsoluble oil was very low in sulfur, enough was treated to give about 2500 cc. of the SOrsoluble oil. This had a specific gravity of 0.941 (23.3 Be.) and a boiling point range of 198" to 244" C. This 2500 cc. of soluble oil was subjected to repeated fractional distillation a t 5 mm. pressure. (It had been discovered in the preliminary work that some decomposition and some polymerization occurred when these fractions were distilled a t atmospheric pressure.) In this way four 'main fractions were accumulated. Table I gives the results of an analysis of these fractions. Molecular weights were determined by the freezing point method, using recrystallized benzene. The individual fractions were cooled down by a mixture of alcohol and carbon dioxide snow to ascertain their melting points. Practically the entire fraction solidified within a range of 2" C. Temperatures were taken by means of a toluene thermometer, and- are not corrected: I, -70" C.; 11, -65" C.; 111, -48" C.; IV, -28' C. They are without doubt more accurate than the purity of the fractions. Fraction 11, when nitrated, gave, as in other experiments, a dark red, viscous liquid which could not be crystallized. (The reaction with concentrated acid was as violent as in preliminary experiments.) It was soluble in sodium hydroxide or sodium bicarbonate, being reprecipitated by acids. A nitrogen determination gave 9.55 per cent nitrogen, the calculated value for C14Hls (NO& being 10.05 per cent. Further nitration with fuming nitric acid caused little change in the appearance of the nitrated substance and added no more NOz radicals. Exposure to the air caused a gradual decomposition, evolving nitrous oxide and leaving a lustrous, resin-like body. Traces of acid catalyzed this decomposition. An ether solution, after being washed free of acid, remained perfectly stable for months. An attempt was made to reduce some of this nitrated substance by hydrogen sulfide and by action of hydrochloric acid on granulated tin. NO amines could be recovered from the tarry mass left after either reduction.
o :oio
0 (by Molecular Difference) Weight
0:$5 0.52 0.87 0.78 0.32
...
182 179
... 191
...
Calculated Molecular Weight 162 188 174 186
raira
Suggested Formula
Molecular Weight
CiaHis CisHn
182
....
.... C14HZ8
....
lii
...
196
...
It is almost impossible to get data from the literature on compounds similar to those met with in this work. Their odor very closely resembles the naphthalene oil cut from coal tar and it is believed that they are partly hydrogenated substituted naphthalenes. Their specific gravity, index of refraction, carbon-hydrogen ratio, and boiling points clearly eliminate the cyclohexane derivatives and the olefins. With the exception of Fraction I the benzene derivatives are likewise eliminated. A search through Beilstein, Engler-Hofer, Abegg, and Chemical Abstracts resulted in finding only a few references to compounds similar to those suggested, and the properties given for those are similar to the ones found in this laboratory. No other class of compounds which would include those studied here could be found. If the writer's assumptions were correct, I would be a substituted hexahydronaphthalene, I1 and 111 substituted tetrahydronaphthalenes, and IV a substituted dihydronaphthalene. The SOrinsoluble oil was also subjected to repeated fractional distillation under a pressure of 5 mm. These cuts were practically unaffected by 66" Be. sulfuric acid, and had a very pleasant odor and a low sulfur content. Table I1 gives the analysis of these fractions. The index of refraction, as well as the analysis of these compounds, indicates that they belong to the C,HZ, series and that paraffin hydrocarbons are largely, if not entirely, absent. A further evidence of the absence of paraffin hydrocarbons is found in the melting points, which were determined as described above: 11, -43" C.; V, -29" C.; VI, -29" C. Their inactivity toward sulfuric acid makes it almost certain that they belong to the cyclohexane series. ACKNOWLEDO~NT The writer wishes to acknowledge his indebtedness to 8. A. Montgomery and R. S. Lane for invaluable assistance rendered in this work, and to Leroy McMaster for use of laboratory and library facilities a t Washington University.
Trade Standards A pamphlet entitled "Trade Standards Adopted by the Compressed Air Society" has just been published, embodying the result of extended study and research on the part of the executives and engineers associated with the members of that organization. It embraces the nomenclature and terminology relating to air compressors and their operations; a history of the development of speeds of air compressors; an explanation of capacities and pressures; instructions for the installation and care of air compressors with illustrations of devices suggested for cleaning the intake air; recommendation for the lubrication of air compressing machines and the cleaning of air receiver piping; a description of the low pressure nozzle test recommended by the society, and a partial list of applications of compressed air. Copies may be had from the members or by addressing the secretary of the society, C. H. Rohrbach, 50 Church St., New York, N. Y .
