ON THE ORIGIN OF PETROLEUM

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000100230014-1
• Release Decision: RIPPUB
• Original Classification: R
• Document Page Count: 18
• Document Creation Date: December 22, 2016
• Document Release Date: May 10, 2012
• Sequence Number: 14
• Publication Date: March 6, 1952
• Content Type: REPORT

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On the Origin of Petrbleum
L. K. Osnitskaya3
Prirodal No 4, pages 13-203
Moscow/Leningrad: April 1946.
STAT
STAT
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ON THE ORIGIN OF PETROLEUM
L. K. Osnitskaya
Petroleum and the products of processing it are an extremely
important raw material in the modern people's economy, Several
hundreds of millions of bons of petroleum are consumed annually by
auto-transport, aviation, the fleet, and the chemical industry.
The importance of petroleum in the country's economy was understood
long ago, and therefore the study of the properties of petroleum
and its origin, its formation in natural conditions, have received
great attention from investigators since the times of old.
Back in. 1763 Lomonosov, as if he were foreseeing the develop-
ment of science and. economics 150 years in the future, expressed the
idea that the mother substance of petroleum is peat, which produces
petroleum products under the action of high temperature.
A. subsequent attempt to determine how petroleum could come
into existence was made by a member of the St. Petersburg Academy
of Sciences, Pallas, who decided that petroleum was formed as a
result of the dry distillation of hard coal located in the bosom of
the earth.
However, in 1863 the Russian academician Abikh, studying a
deposit of petroleum on the Apsheronskiy Peninsula, came to the
conclusion that Pallasts point of view was erroneous since the gases
found with petroleum do not contain carbon monoxide) which is always
found in the gases of the dry distillation of coal. The entire
aspect of occurrence of petroleum deposits permitted Abikh to think
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that shales lowered deep into the earth could be subjected to heating
which caused the appearance of vapors which rise through cracks and
yield petroleum deposits in porous receptacles in the earth. How-
ever, since the processes of distillation of shales assumed by Abikh
were not actually observed, Abikh did not insist on his theory, and
as soon as Mendeleyev suggested a theory of the mineral origin of
petroleum in 1877 Abikh immediately adopted the Mendeleyevian theory.
Mendeleyevis theory came into being on the oasis of the work
of the French chemists Berthelot and Boisson. In 1863 Berthelot
expressed the hypothesis that the core of the earth consists of
alkali metals exposed to the action of carbonic acid and carbonates,
as a result of which carbides are formed; the latter, under the
action of water, yield acetylene, which is condensed into liquid
hydrocarbons, yielding as a result of further transformations petro-
leum, which soaks through cracks and accumulates in porous receptacles
in the earth. Berthelotis erroneous assumption that the inner part
of the earth consists of alkali metals was replaced by Boisson with
the assumption that within the earth there is iron which, as a result
of the action of solutions of carbonates, yields hydrocarbons, and
that the latter are liquefied due to condensation or chemical pro-
cesses of densification and form petroleum.
Mendeleyev analyzed the facts more precisely, and therefore
the theory created by him was quite logical. On the basis of the
degree of density of the earth and the properties of chemical ele-
ments he came to the conclusion that the earthts center consists of
carbides. It is known that carbides are found in large quantity in
meteorites, and it may therefore be assumed that when the formation
of the earth from a liquid mass took place carbon could be combined
with metallic iron and yield carbides, which after the formation of
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the earthts crust could yield gaseous and liquid hydrocarbons under
the action of water. Subsequently additional reactions took place)
as the result of which petroleum deposits appeared. The geological
circumstances of the Apsheronskiy Peninsula made it possible in the
light of existing views to acknowledge the correctness of such a
picture. Research. by chemists showed that under the action of water
on carbides (cast-iron, for example) liquid and gaseous hydrocarbons
are formed) which can be condensed and yield mixtures of hydrocarbons
similar to petroleum. Such, in brief, is the theory of the mineral
origin of petroleum, which received widespread dissemination due to
the fact that it was comprehensible to chemists, on the one hand, and
on the other hand gave geologists a means for searching for new petro-
leum deposits. According to this theory petroleum should be sought
at the sites of pronounced depressions, which cause the appearance
in the earthts crust of cracks along which water would move toward the
incandescent center of the earthts core and petroleum would be raised
to the natural receptacles in which we find it, that is, in the foot-
hills of both existing mountain ranges and mountain ranges which
once existed in ancient times. And in fact, quests for petroleum in
such regions were not unsuccessful.
Thus Mendeleyevls theory was progressive and aided the dis-
covery of new deposits and the finding of new chemical reactions.
Although Mendeleyevts theory seems to find confirmation in
experimental data, a
are critical of it.
in opposition to the
whole series of writings have also appeared which
In these writings the following facts are adduced
Mineral theory o.f. the origin of petroleum:
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1. Metal carbides occur so deeply that the penetration of
water to them is greatly hampered.
2. Metal carbides are located in the bosom of the earth at
a temperature of 'several thousand degrees, while petroleum contains,
as was determined later, extremely complex compounds of little
stability (porphyrins), which break down at temperatures above 150-
200 degrees Centigrade.
3. ? Petroleum is encountered mainly in sedimentary rocks of
marine origin. Thus petroleum would have to have moved over great
distances,-while the majority of geologists do not consider this
possible.
Mendeleyevls mineral theory was graduaily supplanted by new
theories of the origin of petroleum, which regarded petroleum as a
product of biogenic origin.
Of such theories we shall mention first of all the theory of
the animal origin of petroleum proposed in 1888 by Engler. Engler
obtained products similar to petroleum as a result of the distilla-
tion of blubber at 360-420 degress Centigrade. On this basis he
assumed that petroleum was formed in the process of distillation of
mainly animal and partially vegetable residues buried in the earth?
At first this theory was figured on a par with Mendeleyevls
theory by certain geologists, but later it acquired ever greater
individual weight. However, the discovery by Walden in 1893, and
again later by Hakuzin in 1904, of the optical action of petroleum,
which had been observed by Biot back in 1835 and at once forgotten,
and the later discovery by Treybs and Orlov (1933) of porphyrins
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(residues of hemin and chlorophyll synthesized by animal or plant
organisms) in petroleums, and also the geological conditions of the
location of petroleum contradicted Englerls distillation theory, too.
Subsequent development of study of the origin of petroleum
by the work of Russian (A. A. Arkhangellskiy, G. M. Mikhaylovskiy?
K. P. Kalitskiy, L. A. Sellskiy, and others) and American (Trask)
geologists, and chemists (V. V. Markovnikov, N. D. Zelinskiy,
S. S. Mametkin), rendered Engler 's theory worthless.
The geological circumstances of petroleum deposits and the
chemical composition and properties of petroleums, which were given
detailed study by numerous schools (the V. V. Markovnikov, N. D.
Zelinskiy, and S. S. Nametkin schools), and later by their adherents
both here and abroad, have shown that petroleum could not be formed
at the temperatures necessary for distillation of organic deposits
or the products of changes in these deposits, as held by Engler,
Potoniye and their adherents. Temperatures of 200 to 250 degrees
Centigrade are the limits at which porphyrins and the rotatory power
of petroleums can be preserved, Sulphur compounds of certain
petroleums begin to break down at still lower temperatures over the
brief time-intervals of laboratory experiments. Therefore, the
distillation theory can be applied only for a very small number of
instances, such as for Scottish petroleum.
Inasmuch as the formation, of petroleum cannot take place at
temperatures exceeding 200 degrees Centigrade, scholars attempted to
replace the temperature factor with the time factor, having calcu-
lated by means of extrapolation on the basis of Arrhenius' law how
ONO
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much time was necessary to obtain petroleum at 200 to 150 degrees
Centigrade. Thus, Seyer and a number of other authors hold that the
reactions necessary for conversion of waxes and fats into petroleum
could be achieved at 150 degrees Centigrade, but in the course of
the geological periods transpiring since the moment that the
materials were buried. However it is not always possible to carry
out such an extrapolation, inasmuch as products formed at 450 to 500
degrees Centigrade might show extremely essential differences from
the products of reactions occurring at 150 degree's Centigrade.
In studying the conditions of occurrence of petroleum
deposits) geologists have not succeeded in finding indications of
the accumulation of a layer of buried animals, required by Engler'
theory,..
Lecret? back in 1866, designated sea-weeds as a source mate-
rial for the formation of petroleum. Mikhaylovskiy, Jeffrey,
Hakuzin, Ipatryev, Watts, Sellskiy, Arkhangellskiy) Kreychi-Graf,
Potonlye, Kalitskiy, Lilley, Porfirlyev, Gubkin, Stadnikov, and
others have been in agreement with this view (at times with an
additional assumption as to the possible participation of animal
remains in this process).
Certain of these investigators advance extremely weighty
evidence that the basic role of the mother substance in the formation
of petroleum from marine plant remains was played by sediments of
vegetable remains on the floor of littoral salt-water or partially
enclosed basins.
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A particularly graphic picture of the original stage of
formation of petroleum from marine vegetable remains was given by
G. M. Mikhaylovskiy in 1906. In his opinion there took place in
littoral zones a rapid precipitation of limestone-clay silt to-
gether with the remains of various organisms of the animal and
vegetable kingdom; as the result of covering by succeeding layers
an anaerobic decomposition of the remains of the organisms took .
place in the deposits under the action of bacteria. Afterwards
bituminization took place under the action of solutions of mineral
salts and increased temperature. Thus, back in 1906 direct indica-
tions were made as to the participation of microorganisms in the
formation of petroleum. Later a number of inJestigators
Arkhangeltskiy, Seltskiy, Porfirlyev on the basis of the dis-
covery by Bastin and Ginzburg-Karagicheva (1926) of bacteria in
oetroleums and the liquids occurring with theia, developed the idea
of the participation of bacteria in petroleum formation, assuming
that complete transformation of vegetable material deposited in a
salt-water basin into oetroleum could occur in greatest part as a
result of biochemical processes of reduction and hydration accom-
panied by the smashing of molecules, facilitated by increased
pressure and temperature. The products of reduction which formed,
depending on the conditions of formation of petroleum, as a result
of the processes of orogenesis, migrated together with gas and
water along the cavities of tectonic faults and formed secondary
accumulations in the porous rocks of natural receptacles.
However, although there are data concerning the modification
of fats under the action of bacteria given off by petroleum thus,
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according to Rodinovats studies the process takes place in the ?
direction of the formation of free fatty acids, polymerization of
them, increase in the quantity of unsaponifiables, and transition of
the saturated fatty acids into unsaturated ones ti Il, there has.
not been until recent times knowledge of the facts of the action of
the bacteria -which cause breakdown into light hydrocarbons, reduc-
tion of double compounds, hydroxyls, and ketone groups, and other
processes which should take place in the conversion of the mother
substance into petroleum, in other words, there are as yet no foun-
dations to assert that the basic processes of formation of petroleum
can ?be achieved only by bacteria. It has been established that
bacteria: (a) hydrolyze cellulose, (b) convert glucose into lower
alcohols and fatty acids, (c) saponify fats, (d) reduce saturated
acids into non-saturated ones, (e) decompose the higher fatty acids
to lower ones, (f) polymerize unsaturated fatty acids, and (g) oxi-
dize hydrocarbons due to the oxygen of the air and sulphates. In
recent times Tsobell and Yankovskiyls report has appeared, to the
effect that under the influence of desulphurizing bacteria from
fatty acids (propionic, butyric, caprylic, and other acids) oils
containing hyrOCarb011S of the aliphatic series are formed.
In 1927 A. la. Arkhangeltskiy wrote that the precipitation of
argillaceous sediments, which provided the foundation of petroleum
-
producing layers, occurred in marine basins in which deep strata were
infected through hydrogen-sulphide fermentation.
Analogous pictures of the first stage of formation of petro-
leum were painted by Kreychi-Graf, Potonlye, Porfirlyev Kalitskiy,
and Lilley. In their conceptions the organic mass of salt-water
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basins, as a result of the biochemical processes of decarboxyliza-
tion (anaerobic fermentation) which occurred in the absence of
oxygen, was made poorer in oxygen by comparison with the original
material. In the presence of oxygen or in fresh-water basins the
process of decomposition ended either with complete disappearance
of the organic substance or by formation of comparatively poor-in-
hydrogen fuel shales, or with the formation of various types of
coal. Geologists have succeeded in checking these processes rather
closely.
G. L. Stadnikov, on the basis of analysis of the behavior of
vegetable remains buried in a salt-water basin, imagined the forma-
tion of primary petroleum in the following manner. Primary petroleum
is a product of the decarboxylization of polymerizers of liquid
acids, humus acids dissolved and dispersed in a mixture of waxes,
tars, and unchanged fatty acids in the form of a homogeneous semi-
liquid mass.
Of interest is the scheme of the formation of petroleum
hypothesized by Dobryanskiy, who established changes, in conformity
to principle, of caustobiolites in two directions: (1) from vege-
table remainst shale --4.asphalt _petroleum and (2) from sapropel:
shale?tsapropelite--asphalt --ppetroleum. However, each of the
assumed stages of formation petroleum is already an end substance,
for various reasons undergoing no further modification. It is thermo-
dynamically impossible to assume that the polymers and tars composing
these substances could be transformed, without the action of any
agents and only through the process of time, into petroleum at law
temperatures.
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Berlts theory of the origin of petroleum from cellulose
received rather widespread dissemination. Berl and his associates
demonstrated that with treatment of cellulose at 310 to LOU degrees
Centigrade with alkalis and carbonates (dolomite and chalk) it turns
into plastic (at times a greasy or liquid) mass enriched with hydro-
gen and oxygen, which contains about 78-85 percent carbon, 12-13 per-
cent hydrogen, 2-9 percent oxygen instead of the 423.2 percent carbon,
6.4 percent hydrogen, and 49.4 percent oxygen in the original cellu-
lose. With hydration of this mass with hydrogen under pressure in
the presence of iron and iodine as catalysts, Berl obtained petroleum-
like substances. Berl suggested that proto-petroleum could be formed
as a result of basic hydrolysis of cellulose, and that petroleum was
then formed from proto-petroleum as a result of reduction by the
hydrogen given off in the action of water on ferrous oxide, siderite,
or iron sulphides. Berl demonstrated that the action of water on
these substances leads to the formation of hydrogen. However, Berl
did nob succeed in proving that reduction takes place in the action
of water on the mixture of hydrogen-generating iron compound with
proto-petroleum and water. Still, Berl held that under natural con-
ditions the reduction of proto-petroleum can occur under the influence
of the catalytic action of rocks and salts contained in the water (in
particular, iodine salts).
Berits theory also requires high temperatures for conversion
of vegetable material into proto-petroleum, and that is its most
vulnerable point. However, if it were possible to reduce the temper-
ature of Berlts reaction to 200 degrees Centigrade or lower through
application of a catalyst, this theory would then acquire rights of
citizenship.
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Thus, although there still remain problems which have not been
completely solved as to the nature of material (sea-weed, diatoms,
marine grass, or other plants) deposited and then subjected to trans-
formation into petroleum, the mineral deposits which accompany it,
the degree of salinity of the water in the basin, and also the depth
at which the transformation of organic remains takes place under the
influence of bacteria in conditions of anaerobic fermentation, the
primary stage of the formation of petroleum in salt-water basins does
not call for serious doubts at the present time.
The second stage of the formation of petroleum -- the trans-
formation of proto-petroleum into petrolautm -- is imagined differently
by different investigators. Part of them assume that further forma-
tion of petroleum from primary petroleum occurs as the result of
distillation at high temperature, developed due to the near-by passage
of magmatic masses or the deep depression of the deposits. However,
as already pointed out above, high temperatures should be excluded
from the conditions of the formation of petroleum.
In the opinion of others, the formation of petroleum occurs
as the result of the forcing of the petroleum out of the mother rock
into the porous rock o the collector. However, high pressure cannot
in itself play a serious role in petroleum formation. At this point
mention should be made of the theory of petroleum-producing strata.
Certain geologists, on the basis of consideration of L;he conditions
of occurrence of petroleum, reach the conclusion that petroleum was
formed from clay-containing silts. Thus I. M. Gubkin writes that in
the Maykop deposit, below the basic petroleum deposits, among a series
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of foraminiferous layers there occur beds of highly bituminous clay
with droplets of petroleum scattered through the entire bed. If
these were overlapped or underlain by a porous stratum, there would
then in his opinion be a petroleum-bearing horizon there, and not
just strata with diffusely scattered petroleum. Analogous thoughts
have been expressed by Kreychi-Graf and Arkhangellskiy. The latter,
investigating a petroleum deposit in the northern Caucasus, arrived
at the conclusion that the petroleum had been formed due to the
organic substance of the argillaceous rocks and that the sandy layers
were only collectors on the strength of their porosity, and that the
petroleum had migrated to them. Meanwhile, in cases where the mother
rock is at the same time also porous, or cut by cracks, the petroleum
should from this standpoint remain in the strata were it formed.
The theory of petroleum-producing layers has been exposed to
basic criticism on the part of a number of scholars. For example,
Porfirlyev holds that, while answering all demands on the part of
geology, this theory has a weak place
???? 411,411
the movement of the bitumi-
nous substance found in clays in a scattered state and at the same
time in the form of kerogen into the sands where this substance is
observed in the form of petroleum. Keroen is a form of polymerizer
of fatty acids with humus acids, Lars, and a number of other compo-
nents scattered in them, and extremely remote in its physical and
chemical properties from petroleum. However, at the present time,
as we shall see below, there are no bases for considering impossible
the transition of kerogen into petroleum in the presence of suitable
catalyzers.
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Since far-off times the assumptions have been expressed that
in the process of formation of petroleum catalysis could play a role
(Kreychi-Graf, Potonlye, Nametkin). However, only N. D. Zelinskiy,
in the period from 1927 to 1931 succeeded in a number of brilliant
works in proving that from a whole series of the products encountered
in vegetable and animal residues at temperatures close to 200 degrees
Centigrade substances which are found in petroleums and petroleum-
like materials are 'formed as the result of the catalytic action of
aluminum chloride. These works showed clearly the path which must
be followed in searching for a solution of the problem of the forma-
tion of petroleum.
In 1927 Kobayashi and Yamamoto also approached the problem of
the catalytic nature of the formation of petroleum. They set up
experiments for the recovery of petroleum-like substances from fish
fat under the action of Japanese acid clays, but the experiments
were performed at 500 degrees Centigrade and the petroleum-like liquid
that they obtained was he usual product of the thermal breakdown of
fish fat.
The work of the Russian scientists Gurvich (1912) and Lebedev
(1925-1935) showed that clays, floridine, acid Japanese earths and
other substances also act like aluminum chloride and bromide, boron
fluoride, and other catalyzers known in chemistry, which break down
rapidly in contact with rocks and moisture. Through the work of the
Russian scientist A. V. Frost (196-1940) the low-temperature cata-
lytic action of aluminum silicates and aluminum chloride on hydro-
carbons was confirmed. At the same time: (1) at low temperatures
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polymerization of olefines takes place, (2) at increased temperature
the process of polymerization is accompanied by isomerization and
disproportioning of hydrogen, (3) at higher temperature breakdown
of the saturated hydrocarbons takes place. Through subsequent
experiments the author demonstrated that a number of clays, in con-
tact with organic substances, even at low temperatures have a cata-
lytic effect on the reactions of dehydration of alcohols, elimination
of water from ketones, polymerization, disproportioning of hydrogen
which leads to hydration of light olefines due to loss of hydrogen
by part of the suDstance with the formation of heavy, poor-in-hydrogen
substances which undergo the sorbating action of the clays. All
this, in A. V. Frost's opinion, shows
100 to 200 degrees Centigrade, in the
sufficient measure; the conversion of
biochemical or basic change vegetable
that in the temperature range
presence of active clays in
a number of products of the
residues can produce petroleum
like oroducts. The fact that in certain deposits (for example, the
second Baku deposit) petroleum is not associated with clays cannot
serve as refutation of the hypothesis expressed, since in such places
other substances may be catalysts.
Taking the work done earlier in this field together with the
data which he obtained, A. V. Frost draws two diagrams of the forma-
tion of petroleum in the bosom of the earth. According to the first,
in the author's opinion the less probable, hydrolysis of vegetable
(rich in cellulose) and animal residues by alkali water takes place
at a temperature of about 200 degrees Centigrade under pressure, in
agreement with Berl, and products poor in hydrogen are formed which
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are not soluble in water and which rise above the water layer and
in contact with the clay, losing hydrogen in the form of water.
These products, also under the influence of clays, are exposed to
processes of disproportioning of hydrogen being transformed into
petroleum. The second diagram is represented by the author in the
following manner. Considerable quantitites of dead marine plants
and animals, mixed with clay and sand and the flinty and calcified
skeletons of organisms, accumulate in a salt-rater basin isolated
from the open sea. The residues are subjected to anaerobic destruc-
tion by bacteria. The process of bacterial action is intensified
due to the overlapping i the deposit by -coverings of argil acebuS:
sediments. Deep under the earth, the deposits are heated in conse-
quence to 100 or 150 degrees Centigrade, increasing the speed of
ensuing reactions of a catalytic nature, as a result of which the
products of the breakdown of organic residues consisting of tars,
acids, alcohols; and ketones, are converted into petroleum.
From the attached review of literature it is obvious that the
problem of the origin of petroleum, which has long engaged. the minds
of geologists, chemists, and microbiologists, is at present close to
complete solution. The paths to solution of the basic problems, which
20 years ago were unclarified, have in any case been planned.
(1
READINGS
A. D. Arkhangeltskiy, "Conditions of the Formation of
Petroleum in the Northern Caucasus." M.-L., 1927.
(2) Ginsburg-Karagivheva, "Outlines of the Microbiology of
Petroleum." 1936.
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(3) I. M. Gubkin? "Study of Petroleum", ONTI 1922.
(4) N. D. Zelinskiy? "Selected Works", volumes I and
1941.
(5) A. A. Imshenetskiy, "Microbiological Processes at High
Temperatures", 19424.
(6) K. P. Kalitskiy, "The Geology of Petroleum", 1921.
(7) K. P. Kalitskiy, "Petroleum-Producing Strata", 1934,
(8) K. P. Kalitskiy, "The Origin of Petroleum from the
Residue of Vegetable Groups of the Sea", 1937,
(9) K. P. Kalitskiy, "The Scientific Bases of Quests for
Petroleum", 1944.
19314.
(10) K. Kreychi-Graf, "Basic Problems of Petroleum Geology",
(11) G. M. Mikhaylovskiy, "Certain Reflections on the Origin
of Caucasus Petroleum" Izv. Geolog. Kora., 25, 1906.
(12) S. S. Nametkin, "The Chemistry of Petroleum", 1939.
(13) V. B. Profirlyev? "The Problem of Petroleum Formation
in the Light of Recent Data", Gostoptekhizdat, 1941.
(1)1) R. Potonlye, "The Origin of Coals and Other Causto-
biolites", 1934,
(15) K. F. Rodionova, "On the Transformation of Fatty Sub-
stances by the Microbes of Petroleum and Deep-Water Silts of the
Black Sea", Arkiv IGI, No 70, 1939.
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(16) G. L. Stadnikov, "The Origin of Coals and Petroleum",
lad. AN SSSR, 1937.
(17) A. V. Frost, "The Role of Clays in the Transformation
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Institute of Microbiology
of AN of the USSR
Moscow
17
Declassified in Part - Sanitized Copy Approved for Release 2012/05/10: CIA-RDP82-00039R000100230014-1