Feb., 1 9 1 4
THE J O C R N A L OF I N D r S T R I A L . A N D ENGINEERING CHEMISTRY
different physical properties. T h e presence of such areas implies a lack of continuity i n t h e metal, since t h e junction lines between t h e m are more or less sharp; Figs. 1 9 a n d 20. Such areas when under a load have a tendency t o slip one upon t h e other, t h u s setting u p a rupture. Their presence is revealed microscopically a n d macroscopically b y etching. When studying t h e m under t h e microscope t h e use of t h e lowest powers is advised. Layers, streaks or patches of various impurities as slag, sulfide, etc.-all of these are less ductile a n d more brittle t h a n t h e steel. UETHOD OB EXAMIXATIOX
Sample, polish a n d etch. Examine macroscopically f o r pipes, cracks, seam, laps, blow-holes, honeycomb or sponginess, welds, segregations a n d laminations (especially on t h e cross section), flow lines, excessive slag a n d sulfide areas, cinder, etc., Examine microscopically for lack of uniformity of grain, coarseness, ingotism or incomplete refining. Look for slag a n d sulfide areas with reference t o their abundance a n d distribution. CONCLUSION
I t can be shown t h a t a large piece of work can be spot polished in eight or more different places with b u t little, if a n y , more expense a n d t i m e t h a n it takes t o prepare a s t a n d a r d test bar; t h a t there is a relation between structure a n d physical properties. I t follows t h a t given sufficient experience a n d a set of standards, metallographic methods will give information t h a t cannot be obtained conveniently b y a n y other method of inspection. It should be s t a t e d t h a t metallography is not intended t o replace other methods of test a n d inspection b u t t o supplement t h e m a n d t h u s afford a n additional safeguard against failure. 1423 R . St, WASHINGTON, D. C.
MAHONE PETROLEUM Its Recent Origin, and the Origin of Petroleum in General By CHARLESF. M A B E R Y
Received December 22, 1913
Six years ago I was invited t o visit a section of t h e Valley of t h e Mahoning River in Mahoning County, Ohio, where a deposit of petroleum h a d been known in Milton Township f o r several years, a n d where a n open well was still t o be seen from which oozed a small stream of thick oil. At t h e time of this visit, several wells h a d recently been drilled over a n extended area, a n d were producing a considerable supply of oil. B u t on account of faulty operation a n d mismanagement, these wells soon afterward became inoperative a n d t h e entire field was closed until some years later. Several wells were t h e n t o be seen on a f a r m bordering on t h e river valley, t h e property of ilk. R. Wiesener, f r o m which some years earlier oil had been pumped freely a n d sold as a lubricant without refining. On learning of t h e shallow depths a t which this petroleum was reached, m y interest was naturally aroused with reference t o i t s origin, a n d I made several subsequent visits t o become better acquainted with i t s
IO1
occurrence, in connection with a laboratory s t u d y of t h e oil which seemed especially inviting, for i t evidently differed very materially in its composition f r o m t h e other well known varieties of petroleum. It h a d t h e further attraction t h a t , associated with t h e petroleum i n or near t h e river valley, there were extensive beds of high-grade bituminous coal, sections of which in t h e adjoining Township of Palmyra, were mined on a n extensive scale. I n a narrow section of t h e valley, approximately one hundred feet in width, where t h e river h a d cut i t s way down from a considerable height, exposing a n a b r u p t vertical section of t h e geological formations, a vein was exposed, three or four feet in thickness, of partially weathered carboniferous deposits with t h e accompanying shales so friable t h a t t h e y were easily crushed in t h e hands. Analysis showed t h a t these deposits contained nearly fifty per cent of pure carboniferous material. It, therefore, seemed probable t h a t t h e coal a n d t h e oil were of a common origin, which, in connection with t h e shallow depths of t h e oil s t r a t a , less t h a n I jo ft., presented a n inviting opportunity t o s t u d y t h e origin of petroleum a t close range. GEOLOGICAL OCCURRENCE O F MAHONE P E T R O L E U M
T h e Mahoning River rises in Columbiana County, a n d flowing sinuously through Portage, Trumbull, a n d Mahoning Counties, finally enters t h e Ohio River. I n Mahoning C o u n t y t h e valley is a few miles in length, a n d i t s greatest width is 2800 f t . T h e wells drilled for oil v a r y i n depth from 1 3 5 t o I jo i t . ; i n one well t h e oil sand was reached a t a depth of 11; f t . according t o t h e report of t h e driller, t h e surface layer extends i n a depth of 2 0 f t . t o a bed rock of shales t h a t are continuous t o t h e oil-bearing sand. These shales are partly light a n d partly dark in color, a n d just above t h e upper layer, below t h e surface silt is a bed of sand a n d below t h a t a bed of shale impregnated with bituminous carbon. T h e oil sand composed of rather coarse granules of very pure quartz is overlaid b y a soapstone shale 14 f t . thick. a n d i t extends to a depth of roj ft., of which t h e upper coarser layer, 16-18 ft. thick, carries t h e oil above a large volume of water. Below this sand is a bron-n shale sixty feet thick, a n d below this a lighter shale extending t o t h e Berea Grit. So far as i t appears from t h e 2 j or more wells t h a t have been drilled b y t h e hIahone Oil a n d Gas Company, there are no restricted pockets i n t h e oil s t r a t a , b u t a somewhat regular anticlinal a n d synclinal formation, t h e anticlinals approximately 2 0 f t . in height a n d On account of t h e inertness 200-300 f t . in diameter. of t h e crude oil, special care is necessary in drilling, a n d particularly in pumping: i t is raised with some water into large settling t a n k s a n d t h e water drawn off. T h e daily yield from a single well is small; t h e largest daily o u t p u t from a n y one well has been 8 barrels. There is evidently nothing especially striking in t h e formations connected with t h e occurrence of this petroleum, except t h e shallow depths at which t h e oil is found, a n d t h e absence of a n y complicated conditions connected with i t s origin. As mentioned above, t h e Berea Grit appearing in
T H E J O C R S A L OF I S D r S T K I A L A N D E S G I S E E K I S G CHElMISTRP
I02
this section as a n underlying formation suggested t h e probability t h a t t h e abundance of oil a n d gas elsewhere i n this oil s t r a t a should liken-ise promise similar yields in this field. Accordingly a well was s t a r t e d with t h e intention of drilling t o a sufficient d e p t h t o reach a n y possible deposits in this section of t h e Berea Grit. This well has been carried t o a d e p t h of 1x00 f t . a n d will be continued n-ith t h e expectation of reaching a n a b u n d a n t flow of gas a n d t h e lighter Berea G r i t oil. P H Y S I C A L CHARACTERISTICS A X D C031POSITIOX
OF
MA H 0 N E P E T R 0 L E U 11
Soon after t h e first wells were drilled, specimens of t h e oil placed i n m y hands for examination appeared t o be so unlike a n y t h a t h a d been brought t o m y attention, t h a t I undertook a thorough s t u d y of t h e crude oil a n d t h e products t o be obtained from i t , both on account of its interest from a scientific point of view a n d t h e possibility of t h e preparation from i t of commercial products. After three years with t h e aid of t w o assistants, although much has yet t o be done on t h e composition of its constituents i t seems advisable t o place on record t h e accumulated observations on t h e n a t u r e of t h e crude oil. This petroleum is quite d a r k , approaching black in color a n d i t has scarcely a n y odor. I n consistency i t is very thick a n d viscous; i t s specific gravity t a k e n from samples p u m p e d a t different times during three years gave, a t 20' C., in four samples: I
I1
111
Iv
9057
9036
9040
9036
showing practically n o variation in different sections of t h e field during this period. I t s extremely high viscosity-9~8-explains its former use as a lubricant without refining. I t s refractive index as determined b y t h e Xbbk refractometer is 1.4878, a value unusually high as compared with other varieties of petroleum. So much attention has recently been given t o t h e optical activity of petroleum, a n d rotation has been observed in so m a n y varieties of crude oil a n d products of re-. fining, t h a t i t became necessary t o ascertain whether this petroleum was also optically active; b u t in neither t h e crude oil nor in a n y products separated from i t could t h e slightest effect on t h e polarized r a y be detected. Perhaps this is what should be expected in view of i t s composition which is much less complex t h a n t h a t of other varieties of petroleum, in fact consisting (as will be shown later) of a comparatively few hydrocarbons, so f a r as examined only of t h e series C,H2,-2 a n d C,H2%-4. I n testing t h e crude oil for sulfur b y decomposition with sodium a n d comparing t h e color given b y potassium nitroferrocyanide with colors obtained from oils containing known percentages of sulfur, i t gave a color corresponding t o less t h a n 0.01 per cent.1 Inasmuch as petroleum dissolves sulfur t o t h e ext e n t of 3 per cent there a r e . p r o b a b l y few crude oils 1 This is an extremely delicate test for sulfur in petroleum oils, a n d extremely accurate quantitatively based on the comparative depths of color given by oils with 0.1, 0.01, a n d 0.001 percentages a s standards.
To1 6 , S O .z
t h a t do not contain this element or i t s hydrocarbon derivatives. A wide range of crude oils tested b y this method all gave colors for sulfur except such !ight varieties as those from Pennsylrania, West 1-irginia a n d t h e Berea Grit oils of southern Ohio, all of which consists T-ery largely of t h e series C,H2, + 2 , including t h e solid paraffine hydrocarbons, none of w h k h shom-ed a trace of sulfur. S i t r o g e n is a significant element relating t o t h e formation of petroleum, since it has been assumed t h a t nitrogen compounds i n petroleum could h a r e h a d their source only in organic m a t t e r of animal origin. I n most varieties of American petroleum nitrogen has been identified-to t h e largest extent in California oils. It therefore seemed interesting t o ascertain whether l l a h o n e petroleum contains nitrogen : j grams of t h e oil were subjected t o t h e Kjeldahl method with t h e precaution necessary t o convert all t h e nitrogen of t h e possible pyridine or chinoline compounds into ammonia, a n d t h e resulting solution distilled, a n d Nesslerized. N o trace of color appeared, t h u s excluding nitrogen as a constituent. ,4 specimen of Pennsylvania petroleum tested in t h e same way gave n o t a trace of nitrogen as ammonia. T h e question as t o t h e presence of nitrogen in other varieties of American petroleum will be determined in this manner. Mahone petroleum is unique in composition i n t h a t i t contains no hydrocarbon of t h e series C,H2, + 2, gasoline or kerosene, a n d none of t h e series CnH2, t h a t constitutes so large a proportion of Pennsylvania So f a r as i t can be distilled i i t lubricants. vacuo this oil consists very largely if not entirely of t h e series C,H2, - 2 , a n d t h e series C,H2, - 4. As t o t h e composition of t h e residue of distillation above 350' under 30 mm. pressure nothing can be said, for a t this point or perhaps somewhat lower in temperature t h e hydrocarbons simply fall asunder, having reached t h e limit of their capacity t o maintain molecular composition, a n d t h e distillates come over as thinner oils. These changes are readily a n d accurately detected b y t h e viscosity a n d cold tests of t h e distillates which without warning m a y change in viscosity from 2 5 0 t o less t h a n 100,a n d t h e cold test from - 2 0 t o +IO'. Under atmospheric pressure t h e crude oil begins t o distil a t 2 3 0 ° , a n d a t z j o o i t begins t o decompose, breaking down into thinner oils. I t will be interesting t o ascertain t h e composition of these products of decomposition. If t h e distillation be continued beyond this point, t h e residue consists of a t h i n t a r which, in v a c u o , m a y be r u n down t o within t w o per cent of residue without coking. T h e general distinction of t h e varieties of petroleum, those with a paraffine base a n d those with a n asphaltic base, does not apply t o Mahone petroleum, which contains neither paraffine nor t h e so-called asphaltic hydrocarbons. While t h e crude oil contains no crystalline hydrocarbons ( a t least none were observed a t a temperature of -zoo) when decomposition is caused b y distillation, crystalline hydrocarbons appear in t h e residue, a n d in t h e higher distillates. There is a close connection between t h e formation of these
F e b . , 1914
T H E JOl'RS.1L OF I S D L ' S T R I A L A S D E S G I S E E R I S G C H E M I S T R Y
crystalline bodies a n d changes i n t h e cold test. These changes are directly t h e opposite of those which occur under similar conditions in other petroleums where t h e tendency is toward a breaking down of t h e crystalline hydrocarbons into t h i n oils. S e r e r t h e l e s s t h e hydrocarbons in ?\lahone petroleum are remarkably stable in distillation when air is excluded a n d under diminished pressure. Distillates prepared in t h e course of this work were carried apparently unchanged as shown b y analysis through fourteen repetitions, a n d as it seemed, t h e distillations could have been contin ue d indefinitely mit h o u t de co m p osi t i o n ,
103
Carbon, 86.49; Hydrogen, 13.44; required for t h e formula C,,H,,: Carbon, 86.74; Hydrogen, 13.26. Hydrocarbons of t h i s series with such low molecular weights have not hitherto been separated from petroleum. -1 hydrocarbon, C , j H 2 4 rwas identified in this laboratory as a constituent of Santa B a r h a r a , Cal., petroleum, a n d several of t h e same series with much higher molecular weights from Ohio a n d Pennsylvania oils a s constituents of lubricants prepared from these oils. T h e composition of t h e fraction I Z O ' - I ~ I " was shown by its molecular vTeight, 180.4; required for t h e a n d by combustion: CarLon, 86. 7 2 ; Determinations of carbon a n d hydrogen in t h e crude formul&CUH?,: 1 8 0 ~ Hydrogep, 13.33; required: Carbon, 86.66; Hydrogen, oil gave percentages corresponding t o t h e series C n H z n - 2 : C , 86.42; H , 13.31. Assuming a mean com- 13.34; specific gravity: 0.8614. Since t h e hydrocnrposition represented b y t h e formula CloH38. t h e pro- bon separated from S a n t a Earbara oil was collected portions of carbon a n d hydrogen are: C, 86.33; H , 13.67. under 60 m m . a n d none of t h a t product is still on h a n d , To separate t h e constituents of t h e crude oil, so far it cannot be compared with t h e one now under examinaas it can be done b y distillation i i z ' ~ " c z i owithout de- tion. The molecular weight of t h e fraction 13o~-131' was composition, t h e light a n d heavy fractions from five gallons, separated first i n iron stills, mere carried found t o be 194; required for C14H?6, 194. By comthrough a prolonged series of distillations a n d finally bustion it gave: C a r b o n , 86.48; Hydrogen, 13.64; recollected within limits of single degrees under 30 m m . quired: Carbon. 86.60; Hydrogen, 13.40; specific gravity a t z o o ! 0.86 54. T h e lowest fraction came over in t h e vicinity of 90' a n d in q u a n t i t y only I j grams. I t s odor resembled t h a t -1 molecular n-eight determination of t h e fraction of t h e terpenes-quite unlike t h e odors of t h e petro- 138'-139~ gal-e 206.7; required for C I ~ H ~ 208. It R, leum hydrocarbons. -4 somewhat larger a m o u n t , 3 j gave b y combustion: Carbon, 86.38; Hydrogen, 13.64; grams, collected after t h e twelfthdistillation a t 97'-98'. required for CljH?g: Carbon, 86. j 3 ; Hydrogen, 13.46; Fractions also collected in much larger amounts at specific gravity at zoo, 0.8662. The fraction I jr0-152' quite reguiar intervals of IO' as t h e distillation gave as i t s molecular \\-eight, 2 1 8 . 7 ; required for t h e proceeded, as follows: 109'-110', 40 grams; 1 2 0 ' formula C&?g, 218. It g a v e b y combustion t,he follow121'. 7 9 grams; 130'-131', 143 grams; 138'ing percentages of carbon a n d hydrogen: Carbon, 8 . i . o ; ; , grams; 161'-162', 139'. 2 0 7 grams; I ~ I O - I ~ ~ O 300 Hydrogen, I 2.88; required: Carbon, 87.28; Hydrogen, 4 2 j grams; 1 7 1 ' - 1 7 2 ~ , joo grams. At higher tempera- I 2 . 7 2 ; specific gravity a t 20°, 0.869 2. tures there was still a tendency for quantities t o acFor t h e fraction 1 j 1 ~ - 1 7 2 ' was found the molecular cumulate b u t a t somewhat longer limits, I j '. Hitherto, weight 2 3 j ; required for t h e formula C17H30, 234. A good evidence of t h e series C n H z n - ? , a n d CnH2%-4 combustion gave t h e following percentages of carbon in petroleum has been obtained in this laboratory, a n d hydrogen: Carbon, 8 7 . 0 2 ; Hydrogen, 12.90; reb u t t h e results herewith presented are conclusive a n d quired for CliH30: Carbon, 87.18; Hydrogen, 12.82; more comprehensive. T h e series i n Mahone pe- specific gravity a t 2 0 ° , 0.8716. Of t h e higher fractroleum is defined b y analysis. a n d t h e individual hydro- tions to be more fully examined later, t h a t collected carbons b y determinations of their molecular weights, a t 212'-214' gave a s i t s molecular weight 263; which gave very satisfactory results b y reason of corresponding t o t h e formula C19H34, molecular t h e prolonged distillations on which a n assistant was weight 262. I t gave, b y combustion, percentage3 of engaged nearly all his time during twelve months. carbon a n d hydrogen required by this formula: Carbon, All molecular weights Trere determined b y t h e Beck- 8;.1 2 ; Hydrogen, 13.01; required for C19H31: Carbon, m a n n freezing-point method. 87'03; Hydrogen, 12.9;; specific gravity a t z o o , T h e fraction 9 7O-98' was examined n-ith considerable o . S i 9 0 . The series C,H2,z-4 is, therefore, established as constituting much t h e larger p a r t of RIahone interest, for if a n y hydrocarbon of t h e series C,H2, were present in t h e crude oil i t should a p p e a r a t this petroleum so far as this examination extended. I t point B u t its molecular weight was found t o be I j 3 ; appears also t h a t as commercial products 1.ubricnnts calculated for t h e formula C,,Hl0, I j z ; specific g r a v i t y m a y be prepared from this crude oil t h a t shall contain a t 2 0 ' . o.Sj49. Ai combustion gave percentages re- four hydrocarbons, a n d even only t w o . of this quired for t h e same formula: Carbon, 86 76; Hydrogen, single series. This applies likewise t o Texas petroleum 13 26; required for C I I H 2 ~Carbon, : 86.83; Hydrogen, since i t has been found in this laboratory t h a t t h e most 13.26 I t is, therefore, safe t o conclude t h a t t h e series valuable lubricants separated f r o m t h a t c r u d e oilare comC,H?, is n o t present in this petroleum. T h e fraction posed of hydrocarbons of this series, C,2H2n..4, as has collected a t 109~-110" gave as its specific gravity a t also been shon-n for lubricants prepared from California petroleum. 2oo,o 8 j76, a n d as its molecular weight, 166; required for t h e formula C,,H,,, 166. X combustion gave: These results are summarized in t h e folloiTing table:
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
104 Distillation temperatures
Sp. gr. at 20’ C.
Actual determinations m i . wt
970-980 109°-1100 120 0-1 2 1 130 “-1 3 1 138’-139’ 151°-1520 171°-1720 2 12 O - 2 14”
0.8549 0.8576 0.8614 0.8654 0.8662 0,8692 0.8716 0.8790
86.76 153 166 86.49 1 8 0 . 4 86.72 194 86.48 206.7 86.38 218.7 8 7 . 0 7 233 87.02 263 87.12
H
C
13.26 13.44 13.33 13.64 13.64 12.88 12.90 13.01
Required
for
CioHzo CizHzz Ci~Hzd CiiHx CiaHzs CieHzs CllHsO CiaHal
Mol. wt. 152 166 180 194 208 218 234 262
C
H
86.84 86.74 86.66 86.60 86.54 87.28 87.18 87.03
13.16 13.26 13.34 13.40 13.46 12.72 12.02 12.97
The higher fractions will be more fully examined later. I N D E X O F REFRACTION
Three specimens of t h e crude oil collected in differe n t years a n d from different wells gave t h e ‘ following indices of refraction in a n Abbe refractometer a t 2 6 O : I
I1
I11
1,4878
1.4878
1 ,4882
Fractions obtained by prolonged distillation described above gave t h e following indices:
as
800-810 . . . . . . . . . . 1 ,4499 97’-98’ . . . . . . . . . . 1 ,4570 12oc-1210 . . . . . . . . . . 1 ,4625 138 O- 139 O . . . . . . . . . . 1 ,4645 15 1°-1520. . . . . . . . . . 1 ,4688 230°-265’. , . , . , , , , . 1 ,4820 265 ‘-3 15’. . . . . . . . . . 1 ,4879
These results were obtained after ‘treatment with sulfuric acid; t h e indices were t h e same before a n d after this treatment. ORIGIN O F MAHONE PETROLEUM
The question of t h e origin of petroleum has received profound attention both from geologists a n d chemists, b u t it is yet elusive on account of t h e difficulty of securing reliable d a t a t h a t should explain t h e conditions under which i t was formed, a n d of accounting for t h e several series of hydrocarbons of which it is composed. Then, further, t h e absence of organic material a s a possible source, a n d t h e geological disturbances associated with its present situation afford too meager information f o r its complete elucidation. I n t h e petroleum under consideration several of these uncertain features were eliminated. I n t h e first place, t h e shallow depths of t h e oil s t r a t a a n d its apparent common origin from vegetation with t h e extensive beds of coal close a t hand indicate a more recent formation of these oil deposits t h a n can be assigned t o other well known varieties t h a t occur a t greater depths. I n t h e Mahone field, t h e oil sand has evidently not been disturbed since t h e oil was therein accumulated. T h e neighboring coal s t r a t a suggested a coincident formation of t h e oil as a n intermediary product between vegetation and coal a n d t h a t subsequent geological conditions of heat a n d pressure forced out t h e liquid hydrocarbons forming t h e oil deposits as t h e y now appear. This view of its origin is supported by recent experimental evidence. Pictet a n d Bouvier’ distilled Montrambert (Loire) coal under I 5-1 7 mm. pressure, a n d fractionated t h e t a r . They isolated two hydrocarbons, CloHzo a n d CllH22, which they found t o be identical with hydrocarbons separated from Cana1
Rer. d . chem. Ges., Nov., 1913, 3342.
Vol. 6 , N o .
2
dian petroleum. After giving t h e closely agreeing values as t o specific gravity, molecular weights, and refractive indices, t h e y summarized t h e comparison as follows: “Vergleicht man nun die von Mabery engegebenen Eigenschaften dieser beiden Fraktionen mit dienen unserer Kohlenwasserstoffe CIOHZOund HZZ aus dem Vakuumteer, so sieht man, dass sie sich ebenfalls fast genau decken. Die Uebereinstimmung ist eine so gute, dass man daran nicht zweifeln kann, dass es sich nicht mehr u m isomere, sondern u m identische Korper handelt, u n d dass im canadischen Petroleum und i m Vakuumteer der Steinkohle von Montrambert dieselben Kohlenwasserstoffe CloHzo und C21H22 vorhanden sind. Mit andren Worten werden durch Vakuumdistillation gewisser Steinkohlen Korper gewonnen, die sich anderswo als Bestandteile gewisser Erdole vorfinden. Somit ist zum ersten Mal ein chemischer Zusammenhang zwischen den beiden Naturprodukten auf experimentellen Wege dargetan.” T h e last important statement may be translated as follows: Therewith for t h e first time is a chemical connection between both these natural products (coal a n d petroleum) established b y experiment. The complete absence of the series C n H z n + 2 is not unusual; those hydrocarbons are wanting in most heavy varieties, b u t t h e series C,H2, is more frequently present.’ I n composition, Mahone petroleum evidently stands between varieties with t h e so-called paraffine base, such as Pennsylvania a n d Ohio on t h e one hand, a n d those with a n asphaltic base such as t h e Texas a n d California varieties on t h e other. The absence of paraffine is significant since i t shows t h a t t h e oil as originally formed has all been converted into series, with less hydrogen. Likewise t h e absence of asphaltic constituents is significant a s indicating t h a t t h e changes in formation have not been such as t o include these bodies poorer in hydrogen, either through t h e agency of heat or pressure, or by t h e prolonged action of sulfur o n t h e atmosphere, which no doubt are concerned with t h e formation of natural asphalts. T h e determining influence of sulfur a n d oxygen in t h e primary formation of t h e principal constituents of petroleum evidently cannot be disregarded in a t tempting t o account for their origin. As mentioned above, t h e heavy varieties of petroleum dissolve sulfur t o t h e extent of three per cent of their weight. I found t h a t one variety of Texas oil, t h e “ H u m b l e Crude, ” contained three per cent of sulfur, t h e greater p a r t as t h e element in mechanical solution. Much t h e larger proportion of t h e world’s supply of petroleum contains sulfur in considerable quantities, in p a r t , in t h e form of hydrocarbon derivatives, such, for example, as compounds of t h e series C,H2,S which were identified in this laboratory as constituents of Ohio, Indiana, a n d Canadian petroleum. I n a paper published several years ago I expressed t h e opinion which was quoted by Engler in “ D a s Erdol,” t h a t petroleum containing sulfur probably had its source in organic remains of animal origin. B u t more recent s t u d y of t h e relations of sulfur a n d petro-
F e b . , 1914
T H E J O L'RiVAL O F I X D L - S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
leum hydrocarbons especially in connection with crude oils from t h e Texas fields makes i t plain t h a t a n y petroleum may contain sulfur whatever its origin, provided it comes in contact with native sulfur which is widely distributed. As is well known a n y hydrocarbon heated with sulf u r loses hydrogen a n d evolves H2S; if t h e hydrocarbon be of t h e series CnH2,+2 it is p r e t t y certain under carefully regulated conditions t h a t t h e hydrocarbon nucleus will combine with more of t h e sulfur b u t this feature of its action has not been fully verified. I n t h e s t u d y of t h e hydrocarbons distilled from coal b y Pictet and Bouvier it was found t h a t H2S was evolved when t h e hydrocarbons were heated with sulfur a n d t h a t sulfur derivatives were formed. On account of t h e instability of t h e sulfur derivatives of the hydrocarbons, unless special care is exercised. it is probable t h a t t h e principal products should be hydrocarbons poorer in hydrogen, such a s t h e series C,Hzn, C,H2, - 2 , C,H2, - 4 , t h a t constitute the main body of petroleum. T h e formation of t h e great quantities of hydrogen sulfide t h a t escape from many oil wells takes place freely under t h e influence of heat a n d pressure; i t may be b y simple contact under pressure in long geological periods. Experimentally b y prolonged heating with sulfur t h e lighter hydrocarbons may be converted into solid asphalts. All natural asphalts contain sulfur t o a greater or less extent, a n d in view of its ready action on t h e hydrocarbons i t is safe t o conclude t h a t it has had much t o d o with their formation. W h a t most impresses a visitor t o t h e great asphalt lake on t h e Island of Trinid a d , is t h e question as t o its formation. On observing close a t hand. however, numerous petroleum wells with a large o u t p u t , a n d bearing in mind t h e large amounts of sulfur contained in these immense- beds of semi-solid bitumen, t h e answer is not far t o seek. T h e instability of t h e petroleum hydrocarbons in presence of air is a m a t t e r of common observation in t h e manipulation of crude oil a n d its products. I n lighter refined oils on standing color reappears. During distillation t h e heavier constituents increase in gravity, finally forming asphaltic residuum a n d coke. The difficulties arising from this influence of oxygen are t h e most perplexing of all t h a t beset t h e arduous duties of the refiner. This action of oxygen on t h e hydrocarbons is t a k e n advantage of in t h e Byerley process for t h e conversion of residuum into hard asphalts by passing air through t h e residuum a t carefully regulated temperatures. Evidently all changes of this n a t u r e with oxygen as with sulfur depend on t h e abstraction of hydrogen; it is doubtful whether under these conditions oxygen enters a t all into combination with t h e hydrocarbon nucleus. While a full explanation of t h e origin of petroleum should include a plausible source of all its constituents, sulfur a n d nitrogen derivatives, phenols, acids, a n d aromatic hydrocarbons, t h e fundamental demand is for a clear s t a t e m e n t based on experimental d a t a concerning t h e principal series of hydrocarbons. T h e unquestionable source of t h e petroleum hydrocarbofis is organic remains either of vegetable or animal origin,
Io;
i t matters little which, for either is experimentally known t o yield hydrocarbons by decomposition. I n one section of oil territory it may have been t h e enormous growth of t h e carboniferous age t h a t gave t h e coal; in other sections i t may have been t h e extensive beds of sea weeds, a n d in still another t h e organic remains of t h e great masses of shells t h a t have formed t h e limestones a n d dolomites. Reichenbach was t h e first t o recognize t h e presence of paraffine in t h e products of decomposition of organic matter, a n d it has since been frequently obtained with its lower congeners from various animal a n d vegetable sources. Breaking down of paraffine into lower members of t h e same series under t h e influence of heat a n d pressure was observed by Thorpe, a n d no doubt this experimental formation is a close duplicate of similar changes produced in long periods of time under natural agencies. Even when heated with exposure t o air, paraffine gradually breaks down t o lower hydrocarbons. It is certain t h a t these changes are not possible in t h e reverse order, t h a t is, t h e production of paraffine from lower hydrocarbons. I n such molecular decompositions by a simple break in t h e hydrocarbon chain, a paraffine hydrocarbon, for example, C ~ S H ~ ? , should give one C12H26, a n d one C13H26, or b y simple loss of hydrogen i t should give CzsH46 of t h e series C,HZn - 4 . Evidently in such decompositions other bodies are formed even proceeding a s far as marsh gas. A great variety of such changes are experimentally possible especially with t h e aid of sulfur or atmospheric oxygen, a n d in t h e e a r t h with t h e aid of natural heat a n d pressure, yielding a s final products t h e asphalts, or proceeding directly from vegetation t o t h e beds of coal. These changes together with possible evaporation doubtless explain why t h e series C,Hzn+ 2 is not found in t h e heavier varieties of petroleum. I n studying t h e characteristics of these series as t h e y appear in extended distillation up t o t h e breaking point, together with their behavior toward oxygen a n d sulfur, one can hardly escape t h e conviction t h a t t h e hydrocarbons which constitute t h e main body of all varieties of petroleum have been formed from organic matter in nature's laboratory by these progressive changes. Certainly a n y a t t e m p t t o account for t h e origin of petroleum must be based on its composition which includes principally t h e series of hydrocarbons above mentioned, a n d t h e fact t h a t changes in composition are always in t h e direction of t h e lower series a n d lower members, with loss of hydrogen. I n t h e origin of Mahone petroleum t h e influence of sulfur was precluded, for t h e oil is practically free from this element. By reason of t h e shallow depths of t h e porous s t r a t a , contact with air was possible with its influence in removing hydrogen, b u t this action did not continue beyond t h e formation of t h e few series of hydrocarbons which t h e crude oil contains, since t h e oil is free from t h e asphaltic hydrocarbons. These porous conditions were likewise favorable for t h e esIts cape of t h e hydrocarbons C,H2, + 2 and C,H*,. proximity t o t h e coal, its shallow occurrence, a n d t h e experimental results of Pictet a n d Bouvier are pretty conclusive evidence t h a t t h e oil was exuded from t h e
I 06
T H E J O r R S d L OF I S D C S T R I J L A S D ESGISEERIiYG C H E M I S T R Y
coal doubtless long subsequent t o its formation, and perhaps with later changes in composition. This connection between Mahone petroleum a n d t h e neighboring coal will receive further attention in this laboratory, together with t h e products of distillation of t h e natural asphalts. On account of t h e simple composition of Mahone petroleum and its freedom from deteriorating bodies it is especially adapted for t h e preparation of superior lubricants. I n t h e absence of gasoline a n d kerosene hydrocarbons, paraffine or other crystalline bodies, TTith due precautions, distillates may be obtained with extremely low cold tests. So long as t h e hydrocarbons C,H2,-4 remain intact t h e y constitute t h e most durable body in lubrication t h a t it is possible t o prepare from petroleum. The lighter hydrocarbons of t h e series C,H2 ,- 2 with lower viscosity, 100’ t o I 2 j ’, have similar qualities. This petroleum, therefore, yields a range of lubricants especially adapted for delicate mechanism from a chronometer t o a sewing machine, a n d t h e y are widely in use a s prepared b y t h e Eagle Lubricant 11an uf acturing Company. With reference t o t h e formation of petroleum in general, no additional evidence concerning its geological occurrence has been forthcoming within recent years. More extended knowledge as t o its composition a n d t h e relations of its constituents have a n important bearing on its origin. All published results a n d opinions bearing on t h e chemical aspects of its origin were recently thoroughly reviewed by Engler ( “ D a s Erdol”, Leipsic, 1912). T h e theory of its formation from carbides, suggested b y Mendel6eff a n d more forcibly presented b y Moissan a n d accepted ten years ago as a plausible theory, is now generally considered as involving too many hypotheses a n d subsequent changes. Earlier views of t h e transportation or migration of petroleum from t h e place of its origin t o other s t r a t a are no longer generally accepted. Filtration was possible of t h e thinner varieties. T h a t Ohio a n d Indiana petroleum was formed from t h e remains of shell fish coincident with t h e formation of its Trenton limestone habitat as ably maintained b y Orton admits of no other explanation. T h e same may be said of Hunt’s views as t o t h e formation of petroleum in t h e Corniferous limestone. Under t h e t e r m bitumen is included natural gas, petroleum, natural asphalts, a n d coal-the “ organoids” (Eng1er)-with a closer similarity betweenthe members of t h e group t h a n has been hitherto admitted, especially in their primal evolution. It seems evident t h a t t h e formation from vegetation of Pennsylvania petroleum as Fell a s of other similar oils which consist mainly of t h e hydrocarbons C,Hzn + 2 , was accompanied b y less chemical change t h a n t h a t of other varieties. T h e vegetable matter first gave paraffine as t h e principal product, which b y natural agencies broke down i n t o lower hydrocarbons. Then Pennsylvania petroleum was not subject t o t h e action of sulfur which has been evidently a n active agent in t h e formation of t h e heavier varieties. Between t h e Pennsylvania t y p e of petroleum a n d t h e asphalts a n d coals there are all stages of x-ariation
v01. 6 , N O . 2
in composition resulting from t h e greater or less chemical changes in t h e primary seriesof hydrocarbons. Since sulfur is associated with all t h e heavier varieties of oil, asphalts, a n d coal, as well as a p a r t of their composition, from what is knou-n concerning its action on t h e hydrocarbons, i t is difficult t o escape t h e conviction t h a t this element was largely instrumental in forming t h e series of hydrocarbons poorer in hydrogen t h a t constitute t h e principal body of all these natural products. Only a moderate increase in temperature is necessary for its action, a n d such temperatures are quite sufficient t o account for t h e loss of hydrogen even t o carbonization as in t h e formation of coal. But since in t h e coals are still t o be found petroleum hydrocarbons, t h e similar origin of coal a n d a t least some varieties of petroleum is evident. Unquestionaby t h e vast deposits of oil in Texas were formed in a manner analogous t o those in Pennsylvania, probably from vegetable matter a n d t h a t through their association with extensive beds of sulfur, t h e series C n H z n + 2 disappeared completely b y conversion into t h e series with less hydrogen including t h e asphaltic hydrocarbons. I n t h e immense fields of California of more recent origin where t h e oil contains large proportions of nitrogen a n d sulfur compounds, aromatic hydrocarbons, a n d a n exceptionally large proportion of asphaltic bodies, there is good evidence of t h e action of sulfur. With reference t o t h e large a m o u n t of nitrogen compounds contained in California petroleum, t h e y could evidently have been formed from vegetation a n d their presence may be explained by their recent origin of which there is undoubted evidence in some of t h e California fields. T h a t t h e older oil deposits in Pennsylvania a n d Texas contain only very small proportions of n i k o g e n compounds, may have resulted from t h e breaking up of these compounds a n d their disappearance in t h e longer periods of time. T h e swarming maggots t h a t have been observed in some California petroleum are doubtless t h e result of bacterial action on t h e products of decayed .vegetation. It, therefore, seems evident t h a t t h e origin of California petroleum must also be looked for chiefly, if not entirely, in t h e decay of vegetation a n d t h a t t h e hydrocarbons of which California oil now consists were formed primarily f r o m t h e series C,Hzn + b y loss of hydrogen. At any rate, whatever conclusion is reached as t o t h e source of t h e bitumens, i t must be in accordance with t h e predominating characteristic of t h e hydrocarbons t o lose hydrogen a n d t o break down from those most highly hydrogenized through lower series t o t h e asphalts a n d even t o coal. It should also account for a closer relationship in origin between t h e deposits of coal, asphalts a n d petroleum t h a n has hitherto been recognized. While these views are evidently in some respects a t variance with those formerly expressed, if as it seems plain, t h e origin of petroleum as well a s of t h e other bitumens, is t o be explained more directly on t h e basis of its composition, a n d t h e chemical changes t o which i t has been subjected in, a n d since, its evolution from organic matter, t h e question as t o its history is
Feb., 1914
T H E JOUR-TTTdL O F I , V D T S T R I A L A &IT D E iVGI L\~EE RI N G C H E M I S T R Y
107
?
divested of m a n y complicating assumptions, a n d greatly simplified. I should acknowledge m y obligations t o N r . James G r a h a m for assistance i n t h e experimental work of this paper.
ANALYSES O F P U R I F I E D COB.4LT
OXIDE
(PERCCSTAGES)
June, 1912 November, 1912 April, 1913
co . . . . . . . . . . . . . . . . . . . 7 1 . 9 9 Fe .................... 0.11 S i . . . . . . . . . . . . . . . . . . . . 0.040 s. . . . . . . . . . . . . . . . . . . . . 0.020 C a . . . . . . . . . . . . . . . . . . . 0.030 SiOz . . . . . . . . . . . . . . . . . . 0 . 1 9
ChsE SCHOOL O F APPLIDD SCIQNCE CLEVEL.4X.D. O H I O
T7.3
71.52 0.2; 0.020
0 10
Trace
Trxe
n .o j i
...
0.15 0 . i')
n. 1s
The oxides corresponding with t h e theoretical formulas would have'cobalt content a s follows: THE PREPARATION O F METALLIC COBALT BY REDUCTION OF THE OXIDE'
Formula Co2O3, . . .
71.1 CoaOi.. . . . . . . . . . . . . . . . i . 3 . 4
By H E R B E R TT. KALMUS
I n connection with t h e work on cobalt i t has been necessary t o prepare considerable quantities of t h e metal in as pure a s t a t e as possible. Nearly 1000 pounds of conimercial black cobalt oxide have been given t o this laboratory for these researches b y t h e Deloro Mining a n d Reduction Co. of Deloro, Ontario, t o whom me t a k e this opportunity of expressing our thanks. T h e writer wishes t o acknowledge t h e x o r k of Messrs. C. Harper, IT. L. Savell, C. TV. D a y a n d R . Wilcox, who, in t h e capacity of research assistants at these laboratories, h a v e done most of t h e actual experimenting. T o Professor S. F. Kirkpatrick of t h e Departm e n t of Metallurgy, Queen's University, t h a n k s are d u e for m a n y valuable suggestions. T h e process for t h e preparation of fairly pure cobalt oxide has been very completely worked out, a n d has been practised on a large scale a t several Canadian smelters. For t h i s reason t h e oxide was chosen as a r a w material from which t o prepare t h e metal. As t h e work progressed, i t became more a n d more apparent t h a t some of t h e uses for cobalt which were being demonstrated a t these laboratories a n d elsewhere, would lead t o t h e preparation of t h e metal in large quantities. Hence, i t became of increasing importance t h a t t h e metallurgy of t h e preparation of t h e metal from t h e oxide be studied, a n d this has been done with greater care t h a n was necessary merely f o r t h e production of t h e quantities required for experimental purposes. There are four i m p o r t a n t reducing agents for obtaining metal!ic cobalt in reasonably pure form from commercial cobalt oxide. T h e y are: I , C a r b o n ; 11, Hydrogen; 111, Carbon Monoxide; IT', Aluminum, T h e C o 3 0 a used2 for these experiments was made f r o m cobalt h y d r a t e , precipitated b y bleach from a cobalt chloride solution. This hydrate, i n contact with t h e atmosphere, is greenish black i n color. It was calcined a t 750' C., yielding a black oxide of approximately t h e composition Co304. This is shown by t h e following analyses, made a t widely different times, which are typical of a large number: Author's abstract of report under the above title to the Canadian Department of Mines. Published b y permission of t h e Director of Mines, Ottawa, Canada. T h e general investigation of the metal cobalt and its alloys, with reference t o finding increased commerc;al usages for them is being conducted a t the School of Mining, Queen's University, Kingston, Ontario. for t h e Mines Branch, Canada Department of Mines. F o r a consideration of t h e yarious oxides of cobalt, including the proof t h a t the black oxide used for these reductions was larselv . the - . C O J O ~see following article, page 115.
Percentage, cobalt
.......
CoaO;. . . . . . . . . . . . . . . . . 7 6 . 0 COO. . . . . . . . . . . . . . . . . . i 8 . 8
It is obvious then, when we t a k e into account t h e portion of t h e sample which is n o t cobalt oxide, t h a t t h e oxide itself is largely C0304. It is not necessary for t h e purpose of our calculations t o assume t h a t this oxide alone is present, for we shall base our computations upon t h e actual analyses as we have found t h e m . However, i n writing t h e reactions throughout this paper, we shall, for simplicity, consider t h e oxide t o be Co304. PURIFICATIOK
O F COBALT OXIDE
Cobalt oxide as we obtained it from t h e smelters, a n d as sold on t h e market, analyzed approximately as follows: Barrel 1
Percentages
Co . . . . . . . . . . . . . . . 70.36 Ni . . . . . . . . . . . . . . . 1.12 Fe . . . . . . . . . . . . . . . 0.82 ............... 0.45 As . . . . . . . . . . . . . . . 0 . 1 0 Si0 . . . . . . . . . . . . . . 0.20 Ca . . . . . . . . . . . . . . 0.50
s.
Barrels 3 a n d 4
Percentages
Co . . . . . . . . . . . . . . 6 9 . 2
Ni.. . . . . . . . . . . . . 1 . 4 Fe . . . . . . . . . . . . . . 0.50 CaO . . . . . . . . . . . . . 0 . 3 7 s . . . . . . . . . . . . . . . 0.54 Insoluble. . . . . . . . 1 . 4 6 A g . . . . . . . . . . . . . . Trace
Analyses, of course, v a r y considerably from one shipment t o a n o t h e r ; t h e above samples are high in F e , S a n d Ca, a n d would be considered b y most smelters as No. 2 grade. Metal produced from oxide analyzing as above, b y t h e method t o be described. is of sufficient p u r i t y for most purposes. This is especially t r u e if lime be added t o t h e melt t o slag off t h e sulfur. HoTverer, for other purposes metal is required in which t h e impurities, nickel, irbn, sulfur, arsenic a n d silica, are reduced t o very small percentages. I n this case it is best t o remove these impurities from t h e oxide before reduction Starting with a crude cobalt oxide, these impurities m a y be reduced as far as is desired by t h e following procedure: sILIca-Dissolve t h e crude oxide in hydrochloric acid according t o t h e reaction: CoaOl 8HC1 = 3CoC12 qHzO C12 This m a y be done best b y heating a n d agitating with steam. If silica is present, i t will not dissolve, a n d m a y be removed b y filtration or decantation. T h e same is t r u e of silicates which are not decomposed b y this t r e a t m e n t . Decomposable silicates would send a certain a m o u n t of silica into solution. which would be thrown out during t h e next step. I R O S ASD ARSESIC-TOt h e cobalt chloride solution formed b y dissolving t h e oxide i n hydrochloric acid,
+
+
+
