Imrovements in the Oxidising of Oils and in Apparatus for the purpose.
Year: 1897

page_text: This Print is in accordance with the Original Specification as it stands after
Amendment (under Section 18 of the Patents, &c. Act, 1883) as allowed by
the decision of the Chief Examiner of the 12th day of August 1898.
Date of Application, 14th Apr.,
1007
Complete Specification Left. 14th Aug., 1897-Accepted, 9th Apr., 1898
Complete Specification Left. 14th Aug.. 1897-Accepted, 9th Apr., 1898
PROVISIONAL SPECIFICATION.
Imrovements in the Oxidising of Oils and in Apparatus for the
purpose.
We, SIGMUND ROSENBLUM, of 28, Victoria Street, Westminster, Consulting
Chemist, SAMUEL RIDEAL, of 28, Victoria Street, Westminster, Consulting Chemist,
and THE COMMERCIAL OZONE SYNDICATE LIMITED, having its Offices at 31, Lom-
bard Street, in the City of London, do hereby declare the nature of this invention
to be as follows:-
This invention relates to the oxidising of oils so as to produce drying oils and
our invention consists of an improved apparatus and improved methods for such
purpose.
According to the ordinary methods of manufacturing drying oils, the oil is
heated either alone or in presence of oxidising substances usually termed dryers.
Ozone has been proposed for effecting this process at a lower temperature and
also a combined action of ozone with the usual dryers but such processes have
only met with limited success. Various well known substances have been pro-
posed as dryers but for the purpose of our invention it is necessary to have dryers
which are soluble in the oil. We have found from experiment that resinates and
linoleates of metals are the best adapted for the purpose.
The apparatus consists of a vessel with means for introducing the oil to be
treated, and with suitable means for the introduction of ozone; the vessel is also
provided with a discharge pipe furnished preferably with branches and holes along
some part of its length inside the vessel, the discharge pipe being furnished with
a rose which discharges the oil in the state of spray into a covered vessel; this
second vessel may also be provided with means for the passage of ozone through
the sprayed oil and is also provided with a return pipe to the first vessel so that
the operation can be conducted over again if required.
In carrying out our invention we fill the first vessel with the oil to be treated
and we add thereto a dryer which is soluble in the oil viz.:-a resinate or linoleate
(for example) of lead or manganese or a mixture of the two, ozone (preferably
obtained in accordance with what is known as Yarnold's method) is then intro-
duced into the vessel until a suitable pressure is obtained. As soon as this pressure
is obtained a tap in the discharge pipe is opened, when the contents of the first
vessel will be discharged in the form of a spray into the second vessel. To further
ozonize the oil, ozone is introduced into the second vessel (preferably in an upward
The ozon-
direction) so that the oil on falling comes in contact with the ozone.
ized oil collected at the bottom can if desired be conducted back to the first vessel
to be treated in a similar way if further oxidation is required.

page_text: We have found by experiment that a mixture of dryers, for example a mixture
of the resinates of lead and of manganese, gives a better effect than the use of either
dryer by itself.
Dated this 14th day of Anril 1897
J. C. MEWBURN & ELLIS,
55 and 56, Chancery Lane, London, Chartered Patent Agents.
Improvements in the Oxidising of Oils and in Apparatus for the
purpose.
We, SIGMUND ROSENBLUM, of 28, Victoria Street, Westminster, Consulting
Chemist, SAMUEL RIDEAL, of 28, Victoria Street, Westminster, Consulting Chemist,
and THE COMMERCIAL OZONE SYNDICATE LIMITED, having its Office at 31, Lom-
bard Street, in the City of London, do hereby declare the nature of this invention
and in what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement:-
This invention relates more particularly to the oxidation of "drying oils,"
so as to produce quick-drying oils for paints, varnishes ctc., or semi-solid products
used in the manufacture of linoleum, indiarubber substitutes and the like.
24
"
According to the ordinary methods of manufacturing drying oils the oil is
heated to a high temperature, either alone or in the presence of certain oxidising
substances, usually termed driers or siccatives," or in the presence of these
driers." and air or oxygen which are introduced under pressure into the oil by
means of perforated coils.
86
Ozone being a strong oxidising agent has been proposed for effecting this process
at a lower temperature and also a combined action of ozone with the usual driers
has been proposed, but such processes have only met with very limited success.
We have found that though ozone, when used for the oxidation of these oils,
produces a considerable increase in their viscosity and their specific gravity, it
does not, even after prolonged treatment, improve their drying properties, thus
showing that the drying property of an oil is independent of its viscosity and
specific gravity.
If ozone is used in conjunction with the ordinary "driers" which have been
proposed for this purpose, the result remains the same, as most of the proposed
driers are insoluble in the oil, and being heavier than the oil, settle to the bottom
of the vessel in which the process is carried out, and therefore do not enter into
the reaction at all. In examining the action of soluble driers we have found
that only two classes of them viz. the resinates and linoleates of certain metals
can be effectively and economically used in combination with ozone for the
oxidation of drying oils at ordinary temperature or at one not exceeding that of
boiling water.
We have devised the following apparatus for this purpose by means of which
it is possible to accomplish our object in a very short time and in a very effective
manner.
In the accompanying drawings:
Figure 1 is a vertical central section of our apparatus.
Figure 2 is an enlarged view of a portion of Figure 1.
Figure 3 is a plan of Figure 2.
A is a cylindrical casing carried by supports A. Below it is a cylindrical
vessel B having an air tight cover B₁; within the vessel is a helical circulation
coil C, the heating medium entering by the pipe C¹ and escaping by the pipe C².

page_text: B2 is a drain cock placed at the bottom of the vessel B to enable the latter to
be drained when desired, and B³ and B are pipes for the admission of oil and
ozone' respectively into the vessel B.
In the casing A and beneath the top cover A³ is provided a hollow conical
mounting A supporting a circular dish D having a vertical annular flange D¹.
In the dish D is another dish D2 somewhat shallower than the former. 1³ is a
space below the dish D2 communicating on the one hand with perforations D
made through the latter near its circumference, and tubular spindles D³ herein-
after again referred to, and on the other hand with the upper portion of the
interior of the vessel B by way of a pipe E controlled by a valve E¹.
A pipe Fin which is a valve F¹ extends upward from a point near the bottom
of the interior of the vessel B through the cover B, the hollow conical mount-
ing A³, and the bottom of the dish 2 to afford communication between the
vessel D and space D6 in the dish D2, which is closed by a cover D7 perforated with
tapered conical holes 18 having their smaller ends uppermost. Tubular
spindles D5 are screwed into the bottom of the dish 13 and have coned upper ends
which extend into the holes D8. There is a passage way through the holes De
around the tapered upper ends of the tubular spindles D³, which latter constitute
passages for the ozone as hereinafter described from the space D³ to points just
below the level of the top of the cover 17; they can be screwed up or down to
regulate the area of the annular passage around them.
G is a pipe controlled by a valve G₁ affording communication between chamber A
and the interior of the vessel B; H is a drain pipe for draining the chamber A.
The operation is as follows:-
The oil to be treated is delivered into the vessel B through the pipe 13 and the
soluble drier or driers can then be added, or these may have been dissolved in the
oil before its delivery into the vessel. The oil is heated if necessary to the desired
temperature by the circulation through the helical coil C of a suitable heating
medium such as steam or heated air. The ozone, which should be free from
moisture or carbonic acid gas is then delivered into the vessel B through the pipe B*
under any desired pressure, say 7 lbs. to the square inch, and the oil is forced up
the pipe Finto the space De while the ozone passes through the pipe E into the
space D³.
A portion of the ozone escapes from the space D³ through the perforations 14
into the interior of the chamber A while the remainder passes through the
spindles D³ and draws oil from the space Do through the tapering annular spaces
of the passages D³. The oil meeting the ozone at the nozzles of the spindles D
is atomised and in the form of a very fine spray is delivered with the gas into the
interior of the chamber A. where it is met by the additional ozone which enters
the vessel through the perforations D*. The oil thus becomes intimately mixed
with the ozone, and thorough oxidation takes place. The ozonised oil then falls
through an atmosphere of ozone to the bottom of the chamber A from whence
it can be conveyed through the pipe G back again to the vessel B for re-treatment.
Ozone additional to that which passes up the pipe E into the chamber A may be
introduced into the latter, if desired, by a suitable supply-pipe. A is a valve
through which the gaseous contents of the chamber A can be withdrawn, for
delivery to an exhaust-pipe or for further use in apparatus similar to that which
is hereinbefore described.
The operation may be repeated as often as found desirable, but we have found
that if the oil is passed through the apparatus six times it is generally sufficiently
oxidised to be used as a quick-drying oil for paints etc.
In comparing the results obtained by means of this apparatus with those
obtained by means of the ordinary apparatus for introducing a gas into an oil,
we find that a certain quantity of oil containing one of the driers specified above
will be converted at ordinary temperatures into a quick drying oil by means of
our apparatus in two hours, whereas by means of the ordinary apparatus it would
take 30 hours.

page_text: By producing a finely divided spray of oil containing one of the above specified
driers in solution intermingled with ozone, we believe the ozone is broken up and
that its active atom of oxygen is at once transmitted to the finely divided particles
of oil, thus enabling it to absorb with the greatest economy the quantity of oxygen
necessary for its complete oxidation or any desired degree of oxidation in a very
short time and at ordinary temperature. Oils obtained by means of this process
are of a very light colour, of high drying properties and perfectly clear, that is,
they do not give any turbid deposits on standing. A further advantage of this
process is, that no loss is experienced in the out-put of the finished product
through decomposition which takes place in all those processes where a high
temperature is employed, but on the contrary a gain of several per cent. is obtained
in the product owing to the absorption of the active atom of oxygen in the ozone.
The driers, used by us in this our invention are the resinates and linoleates of
lead or manganese. We find also that the combination of the salts of the two
metals such as the resinate of lead and manganese or the linoleate of lead and
manganese or the resinate of lead and the linoleate of manganese or the resinate
of manganese and the linoleate of lead will give better results than either of these
salts alone. However for certain purposes such as when a non-darkening oil is
required for very light paints such as zinc-oxide we prefer to use the manganese
salts only.
The quantity of drier used in our process is very small and for a quick-drying
oil does not exceed 2 per cent.
If semi-solid products are to be obtained from drying oils we prefer to use a
higher percentage of the drier and to prolong the treatment. In order to keep the
highly oxidised oils liquid, we maintain an elevated temperature in our apparatus.
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed, we declare that what
we claim is:
1. Oxidising oils by intermingling a jet of ozone and a spray of oil substantially
as described.
2. in the oxidation of drying oils the use in conjunction with ozone of the resi-
nates and linoleates of lead or manganese, or a mixture of such salts of the two
metals as soluble driers substantially as described.
3. In apparatus for oxidising oils the combination of a vessel B with a device
for intermingling oil in the form of spray with ozone.
4. In apparatus for oxidising oils the device for producing concentric jets of
oil and ozone substantially as described and illustrated in Figure 2 of the accom-
panying drawings.
5. The combination and arrangement of parts constituting the complete
apparatus for oxidising oils substantially as described and illustrated in the
accompanying drawings.
1