IMPROVEMENTS IN, AND APPARATUS FOR, TREATING MINERAL OILS, IN ORDER TO RENDER THEM UNINFLAMMABLE AT PREDETERMINED TEM- PERATURES
Year: 1882

page_text: LETTERS PATENT to Ernest de Pass, of the Office for British & Foreign
Patents, 68 Fleet Street, in the City of London, Patent Agent, for an
invention of IMPROVEMENTS IN, AND APPARATUS FOR, TREATING MINERAL
OILS, IN ORDER TO RENDER THEM UNINFLAMMABLE AT PREDETERMINED TEM-
PERATURES A communication from abroad by Gaspard Philippe Joseph
Napoléon Labouret, of 17 Boulevard Saint-Martin, Paris, France
PROVISIONAL SPECIFICATION left by the said Ernest de Pass at the
Office of the Commissioners of Patents on the 22nd April 1882.
ERNEST DE PASS, of the Office for British & Foreign Patents, 68 Fleet Street,
in the City of London, Patent Agent, IMPROVEMENTS IN, AND APPARATUS FOR,
TREATING MINERAL OILS, IN ORDER TO RENDER THEM UNINFLAMMABLE AT PRE-
DETERMINED TEMPERATURES A communication from abroad by Gaspard Philippe
Joseph Napoléon Labouret, of 17 Boulevard Saint-Martin, Paris, France,
The majority of the oils used for lighting purposes are obtained from crude
petroleum, and from gas-tar, and these oils are known in the arts and commerce
as petroleum, coal oil, shale oil, Boghead oil, according to the mineral from which.
the tar has been obtained.
These oils are by no means homogeneous bodies, but are exceedingly complex
combinations of a great number of hydrocarbons, differing from one another in
their density, and by their boiling point.
Now, the method or process to which this invention relates, allows of obtaining,
from the products of the first and second "run" ("jet") obtained in the ordinary
manner, of oils, which will be uninflammable at any predetermined temperature,
up to, say, 95 or 100° C. The said process consists in the application of known
facts, in relation to the distillation of mineral oils, and their combination with the
hereinafter specified processes.
All delay in the ebullition of a liquid may be avoided, and the lowest tem-
perature, at which it will boil, may be more readily attained if a gas, or a vapour,

page_text: The agitation may be effected with any liquid whose vapours will not combine
with those of the liquid to be vaporized, or with this liquid itself.
Agitation by steam may be practised upon crude mineral oils, and on their
distillates, whether isolated or mixed, and either before or after their treatment
by re-agents.
To effect the agitation, the steam must not be injected in a mass, but in a
divided state, and from the lower part of the closed vessel containing the oil
to be vaporized. The upper part of this vessel must be provided with a pipe
connecting it with a refrigerator, which refrigerator may be of any form. The
arrangement which will best serve for the separation of the parts carried over, and
of the steam that has served to carry them over, consists of two refrigerators or
cooling devices, connected together by a T-shaped separating vessel. The vapours,
condensed in the first cooling apparatus, leave by the lower part, enter by the first
arm of the T into the vertical part of the separator, and there, by reason of the
different densities, the light condensed parts float on the top of the water of
condensation, then, in passing through the second arın of the T, will be entirely
cooled in the second refrigerator, or cooling device. The water of condensation
accumulates in the lower part of the separator, and is eliminated by a tap, or a
siphon.
The water of condensation, obtained by cooling, when the vaporized mass
contains water in suspension, is drawn off in the same manuer from the vessel
in which the vaporization has taken place.
It is obvious that, the arrangement and construction of the appliances for
carrying the above described process into practice, are capable of considerable
variation, and that they may be provided with suitable safety devices.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Ernest de Pass in the Great Seal Patent Office on the
19th October 1882.
ERNEST DE 'PASS, of the Office for British and Foreign Patents, 68, Fleet Street,
in the City of London, Patent Agent IMPROVEMENTS IN AND APPARATUS FOR
TREATING MINERAL OILS, IN ORDER TO RENDER THEM UNINFLAMMABLE AT PRE-
DETERMINED TEMPERATURES. Communicated from abroad by Gaspard Philippe
Joseph Napoléon Labouret, of 17 Boulevard Saint-Martin, Paris France.
The greater part of the mineral oils used for lighting purposes are produced
from crude petroleum, others from tars which are residues of distillation in the
manufacture of gas. In trade and commerce these different kinds are known as
petroleum oil, coal-oil, schist or Boghead oil according to the mineral from which
the tar is derived.
Far however from being homogeneous bodies, these oils are very complex
combinations of hydrocarbons of considerable number, differing from one another
by their density and their boiling point.
When a source of sufficient heat is available, the distillation of petroleum can
be carried so far, as to leave in the apparatus a carbonaceous residue only which
is of no importance, whilst the distillation of raw coal oil, schist and Boghead,
however far the operation may be carried, always leaves an important tarry
residue.
In the course of the distilling, traces of smoke are evolved which resist conden-
sation. They are evidence of the decomposition of the material subjected to
distillation, which material is resolved into more volatile (less dense) products
and a small quantity of carbon; the carbon gradually accumulates in the oil,
which remains in the apparatus, perceptibly colours the latter, contributes to the
formation of paraffine and ultimately produces the residues above referred to.
Before the end of the distilling process, when petroleum attains a temperaturo
of 280° to 300° C. and when coal-oil, schist, and Boghead oil attain from 360° to
400° C, the products of distillation become thick and heavy; they contain a
considerable quantity of paraffine. If the temperature of these products is lowered',
they assume a more or less solid, gelatinous state, so that the temperature of the
cooling medium has to be raised to about 25° to liquefy the produced oil, to prevent
choking of the coil and avoid accidents.
For these reasons, and for others hereinafter dealt with, these products of dis-
tillation are classified as products of the first "run," and products of the second
"run." This distinction is maintained whether the distillation is carried to its end
in one and the same apparatus or whether it is stopped before the temperatures
above referred to are reached and the residue be collected in an apparatus suitable
for rapidly subjecting the same to considerably higher temperatures.
For a proper understanding and explanation of the succession of these phenomena,
recourse must be had to chemical theories. During the entire duration of the
distillation, the liquid mass is subjected to increasing temperatures when it reaches
the boiling point of one of the hydrocarbons of which it consists, the temperature
rises again, before the whole of such hydrocarbon is completely expelled, and this
is the case, however slowly the heating may take place. At every moment,
therefore, the vapours accumulated above the surface of the boiling liquid are al
mixture of vapours which are just then being evolved, and of vapours which have
lugged behind, and of others which are in advance. These different hydrocarbons
being presented to one another in the vaporous state either dissolve one another

page_text: reciprocally in condensing, or they follow, under the influence of the heat, the laws
of decomposition and recomposition which the chemist daily encounters in the
laboratory, forming hydrocarbons which range much higher in their series. A
part of the carbon set free sometimes even escapes this recomposition in this case
it is mechanically carried away with the vapours, and is (in a molecular state)
deposited on the walls of the goose-neck of the coil and of the vessel in which the
products are collected.
The refining of petroleum requires only a single treatment, this treatment
comprises two distinct operations.
1. Fractional distillation and the grouping of the products thereof.
2. Washing of the mass produced with sulphuric acid, soda and water.
The refining of coal-oil, schist-oil, or of Boghead, requires two successive treat-
ments. The products of a first distillation after being washed with acid, soda and
water are re-distilled, and the product of this second distillation is in turn washed
in the same manner.
The distillation is effected by heating, either by open fire, or by the circulation
of steam, or even by adding the injection of steam to one or the other of these two
methods of heating. Whichever of these methods of heating bo the one adopted,
the decomposition and re-composition above indicated takes place, so that if the
distillation be arrested even considerably before the above indicated temperatures
-are-attained, it will be observed that the mass remaining in the apparatus contains.
a proportion of carbon and paraffine which is considerably higher than the
proportion of the same substances in the oil submitted to the distillation.
The washing is effected either by mechanically agitating the mass composed of
the oil and the reagent, or by agitation caused through hot or cold air being
injected at the lower part of the apparatus in, which the washing takes place.
The distinction of the products of "first run" and products of the "second
run" hereinabove stated holds good even when the products of distillation are
examined with regard to their un-inflammability.
--Let-it-be-granted-that-the-products are collected fractionally, and that the
fractional parts be even carried to the hundredth part of the volume of the charge
then every fraction, although considerably less complex, as regards the hydro-
carbons which enter into its composition, than the raw material, nevertheless forms
as above seen a reciprocal solution or a combination of several of these hydro-
carbons, so that for each fraction the density, boiling point and the degree of
inflammability depend on the proportions of the component parts.
If the fractions be studied, which together constitute the products of the first
"run," it will be found that their density increases regularly, almost like the figures
in an arithmetical progression. For petroleum oil they range from 675-680 up to
816; for coal-oil, schist oil and boghead from 720-725 up to 860. It will be
found that their boiling point rises gradually; that their temperature of
inflammability, although increasing with less regularity, also rises gradually up to
fixed limits.
If those fractions be examined, which together constitute the product of the
second "run," it will be found that the boiling points rise gradually whilst the
densities increase and rise by periods consisting of increasing, and decreasing
figures. The temperature at which they are inflammable falls rapidly from the
fixed limit to about 20 or 25° and then remains below that temperature.
If these fractions be studied, say as to the kinds of petroleum, or tar (of coal,
schist or boghead) and if to this end fractions of the same rank be compared, in
each of the categories, it will be found that the densities, the boiling points, the
degrees of inflammability, are much lower in the group of petroleum fractions than
in the other groups; the first of these fractions will boil, and are inflammable at
about a zero temperature; these features are wanting in the other groups where
the lowest densities do not descend beyond 720-725.
The degrees of density however which rise above 825-830 are absent in the
petroleum group and occur in great numbers in the fractions obtained with tar

page_text: of coal, schist or of boghead, and the last fractions on cooling set free more and
more considerable quantities of paraffine. Some are solid at the ordinary
temperatures.
If these facts be taken into consideration, it will be clear that it is easy to
manufacture coal oil, schist and boghead oil which will satisfy the regulations as
to inflammability (35°) whilst it is much more difficult to manufacture petroleum
oils that will fulfil the same conditions of inflammability. It will also be clear,
that, to produce with petroleum, oils which will satisfy the same requirements of
un-inflammability, the products of the second "run "would have to be rejected and
of those of the first "run," all fractions which are inflammable at 35° (say of a
density of less than 750) would have to be eliminated as all the fractions which
follow are less volatile and have higher degrees of inflammability. But this mass
of fractions which follow are, as has been hereinabove shown, rendered impure by
traces of carbon and even some traces of paraffine, and this requires a more energetic
treatinent with the re-agents. A much more serious drawback however is that in
proceeding in this manner the yield is entirely sacrificed, and this explains why
refineries, even the American ones, furnish only such petroleum oils as arc
inflammable at about 26°.
Now the process to which this invention relates permits of employing products
of the first and second " run," to obtain oils which are un-inflammable at any pre-
determined temperature up to, say 95 or 100° C. The said process consists in the
application of the facts herein stated in relation to the distillation of mineral oils
and of their combination with the hereinafter specified processes.
All delay in the ebullition of a liquid may be avoided, and the lowest tempera-
ture at which it will boil may be more readily attained if a gas or a vapour be
injected into the mass. If the liquid be cold, relatively slow injection will slowly
and gradually heat the liquid and the successive carbonization of the residues will
be avoided, if however the liquid be submitted to the influence of another source
of heat, the injection and consequent agitation although they reduce the carboni-
zation would not altogether obviate it.
When steam is used for agitating mineral oils, and other means of heating are
excluded the residue after elimination of some of its parts effected either mechani-
cally or by its heating caused exclusively through its being agitated by the steam,
will regain the colour and even the limpidness and transparency of the oil subjected
to vaporization by agitation.
Thus in refining mineral oil and specially petroleum, a product is to be obtained
which is to be un-inflammable at a predetermined temperature, it will be sought
to eliminate all the products of less than a certain density, and to this end it will
be sufficient to inject into the mass, and to agitate the same by steam of a density
much below that which will cause the ebullition of the product of such density.
By carrying out this injection and agitation for the purpose of distilling the
mineral oils to be treated, the product of the second" run "will be considerably
improved, but it will be necessary either to employ superheated steam or the
agitation will have to be continued for a very long time, and this time will rapidly
increase with the density of the products to be eliminated by distillation.
If all the products, resulting from such agitation are condensed on leaving the
apparatus, the aqueous vapour or steain when condensing, will spontaneously
separate from the distillate, or the liquid carried over from the still, and will allow
this latter to be collected for subsequent use. The vaporized part (the residue
remaining in the apparatus) may sometimes contain some suspended aqueous
vapour or steam. Spontaneous cooling, by condensing this small quantity of
aqueous vapour or steam, deterinines in like manner complete separation, and the
product, as above stated, regains the fluidity and limpidity of the liquid that was
subjected to the vaporization, a result which can not be obtained by distillation, as
ordinarily practised.
The agitation may be effected with any liquid whose vapours will not combine
with those of the liquid to be vaporized, or with this liquid itself.

page_text: •
Agitation by aqueous vapour or steam may be practised upon crude mineral oils,
and on their distillates whether isolated or mixed, and either before or after their
treatment by reagents.
To effect the agitation the aqueous vapour or steam must not be injected in a
mass, but in a divided state, and from the lower part of the closed vessel containing
the oil to be vaporized. The upper part of this vessel must be provided with a
pipe connecting it with a refrigerator which refrigerator may be of any form. The
arrangement which will best serve for the separation of the parts carried over and
from the aqueous vapour or stoam that has served to carry them over, consists of
two refrigerators or cooling devices connected together by a T-shaped separating
vessel. The vapours condensed in the first refrigerator leave by the lower part,
enter by the first arm of the T into the vertical part of the separator and there, by
reason of the different densities, the light condensed parts float on the top of the
water of condensation, then in passing through the second arm of the T will be
entirely cooled in the second refrigerator or cooling device. The water of conden-
sation accumulates in the lower part of the separator and may be drawn off by a
tap or a syphon.
The water of condensation, obtained by the cooling, when the vaporized mass
contains water in suspension is drawn off in the same manner from the vessel in
which the vaporization has taken place.
It is obvious that the arrangement and construction of the appliances for carrying
the above described process into practice are capable of considerable variation, and
that they may be provided with suitable safety devices.
Having now described the nature of the invention and in what manner the same
may be performed I declare that I claim, as communicated to me by my foreign
_ Correspondent, -
1. The new process of obtaining from all the products of mineral oils, especially
those of petroleum, oils free from admixtures, and in an un-inflammable condition
(such as not heretofore attainable) by treating_the_said_oils_by_moans of aqueous
vapour or steam in divided jets agitating the oil as herein above specified.
2. The novel application of aqueous vapour or steam in divided jets for separating
by agitation from the mineral oil under treatment, those hydrocarbons whose
presence lowers the degree at which the whole is inflammable; the operations being
completed by cooling which allows of the separation of the hydrocarbons that havo
been carried over and of the aqueous vapour or steam that has served as their
vehicle, and by cooling again, the separation of the steam intermingled with, or in
suspension in the mass of oil that has been vaporized.
3. Any apparatus serving for the treatment of mineral oils by extracting from
them hydrocarbons when such apparatus comprises the combination of one or
several vessels in which the vapour or steam agitates the mass of oil they contain,
with one or several refrigerators or cooling devices serving to condense the vapours
and to collect the hydrocarbons carried over by such vapour or steam; also any
apparatus consisting of one or several vessels for drawing off the water in suspension
with the vaporized mass or for filtering the latter for the purpose of effecting such
separation substantially as set forth.
In witness whereof I the said Ernest de Pass have hereunto set my hand
and seal this Seventeenth day of October, in the year 1882.
חזימת
DLAC