A Process for the Rapid Oxidation of Drying Oils and their Fatty Acids, by Mixing and Airing the same with Pulverised Sub- stances for the Preparation of Linoleum and Cork Sheeting.
Year: 1898

page_text: Date of Application, 25th Mar., 1898
Complete Specification Left, 27th Dec., 1898-Accepted, 24th June, 1899
PROVISIONAL SPECIFICATION.
A Process for the Rapid Oxidation of Drying Oils and their Fatty
Acids, by Mixing and Airing the same with Pulverised Sub-
stances for the Preparation of Linoleum and Cork Sheeting.
I, DR. JOSEPH HERTKORN, of 29, Kalvin Strasse, Berlin, in the German Empire,
Chemist, do hereby declare the nature of this invention to be as follows:-
The reduction of siccative oils to their rubber-like final products has been the
subject of Patents in Great Britain No. 209 of 1860, No. 2057 of 1871 and No. 2845
of 1872. The processes set forth in these Patents have aimed at obtaining a
very intimate contact between the oils when mixed with siccative materials, and
the atmospheric air by the aid of increased temperatures. The object in view
has been attempted to be attained either by forcing air through the heated oil or
allowing the latter in a finely divided condition to pass through heated air;
or the oil has been exposed to the air by pouring it in thin layers on scrim sus-
The viscid or solid mass of oxidized oil
pended or extended in heated rooms.
thus obtained had then to be subdivided into small pieces by means of rollers or
the like and was then melted with a mixture of soft and hard resins and finally
mixed with ochre and pulverized cork. These processes, however, possess various
disadvantages. For instance, the oxidation of the oil if undertaken separately
as above set forth, involves the use of extensive complicated and costly plant
and the working expenses become very high, whilst the output is limited and
moreover the product obtained is either too sticky or else insufficiently cohesive,
conditions caused either by overcharging or by incomplete or not uniform oxida-
tion of the mass. Further, the subsequent mixing with the linoleum filling mass
requires a number of expensive machines and the use of a large plant, and even
then the mixture of the ingredients is in many cases only imperfect.
pass.
My process is devised to obviate these draw backs. I have discovered that
this may be obtained by effecting the oxidation of the siccative oils (with or without
the addition of driers) after admixture thereof with pulverized, bulky, or specifi-
cally light material, through which mixed mass hot air is preferably caused to
A suitable mixture of materials for carrying out my process is the
linoleum filling mass usually employed consisting essentially of pulverized cork
and sawdust. The oxidation of a large quantity of oil can be accomplished in
from one to two hours by this method, whilst by the process usually employed
hitherto days or even months may be necessary. The linoleum mass obtained
by my process is perfectly inodorous, uniformly mixed, oxidized throughout and
highly elastic. The mixture of glutinous matter or substances with the filling
mass is practically perfect. I add certain hard resins in a finely pulverized
or ground condition to the half oxidized mass to increase its cohesive and elastic
qualities. To prevent the spontaneous ignition of the linoleum mass, saturated
with oil as described, I mix with it earthy alkaline oxides or compounds thereof,
or earthy alkaline soaps. These ingredients produce in the linoleum a certain

page_text: hardness and velvet-like smoothness, together with leather-like flexibility and
superior tenacity. In order more clearly to set forth my invention, I have
illustrated in the accompanying drawing which represents diagrammatically
and in plan view one method of constructing a plant suitable for the carry-
ing out of my invention. The operation is preferably conducted as follows:-
The usual amount of colophony as well as from ten to twenty per cent. of resinate
of magnesia is melted with the linseed oil which is boiled together with drying
materials, and the mixture is then whilst still in the hot state pumped into the
reservoir Q. The contents of this reservoir are gradually heated to about
70° C. The reservoir is provided with draw-off cocks g', q², q3 in its sides so placed
as each to draw off a quantity of about 100 kilogrammes. The said cocks are
connected with the supply pipes R, R¹, the former of which pipes is enclosed in
the mixing cylinder or apparatus A and perforated as shewn. The said mixing
cylinder A is preferably a horizontal cylinder constructed of boiler plate and
bedded on a cast-iron frame suitably placed near the mixing rollers. The upper
part of A is provided with a man-hole and also with a hopper C; the said man-
hole is provided with a valve op damper S and the hopper is
provided with a cover M so that by means of these the cylinder A may
he shut off from the outside. The cylinder A is further provided with the funnel
or pipe B having a damper or valve $ and into which a pipe K projects. This
pipe serves to heat the oil. I further provide a receptacle for the condensed
water and a sluice N. The bottom of the cylinder A is provided with a discharge
door G supported on suitable guide rollers along its entire length, and so arranged
as to allow the mixed mass to fall into the iron funnel T when required, and
from thence to the mixing rollers.
The mixing vessel A is provided, moreover, with an agitator constructed as
follows:-
The hollow shaft W passes axially through the apparatus and has attached
to it hollow wings W, W, W³, W, and so forth, bored out on one side. These
wings are placed alternately in opposite directions at an angle of 25° to the
said shaft. At one end of the said shaft W is a belt pulley E which can be
driven at the required speed from a prime mover of any kind. The other end
of the shaft W terminates in a stuffing box D to which is likewise connected the
air pipe c, and the carbonio acid gas receptacle c. Through the air tube 3
compressed air is driven, and may, if required, be supplied heated to 70°
Centigrade. For this purpose there is provided a heating apparatus, such for
instance as that indicated in the diagram at H through which the air is forced
from an outside source of supply through 3, then through the heating apparatus H
and back to the agitator through the lower pipe in the direction indicated by
the arrow. The heating apparatus shewn is intended to be heated by steam
passing through the coil or serpentine pipe indicated, to a steam trap on the
outside of the apparatus. Suitable valves c c² are provided in the forked pipe c³
for the regulation of the supply of air and its temperature, and are automatically
controlled by the electrical device shewn. The steam heating device H is prefer-
ably heated by steam at from 7 to 10 atmospheres pressure. The electrical heat
regulator is constructed as follows:
Frepresents a tube containing a mercury column having a bulb at its lower end,
and an expanded container at the top. The tube F passes into the interior of the
agitator W and its expanded top projects above the same; this part is calibrated
and graduated and within it are suitably placed the terminals m, n, and the
lowermost connection 2. The maximum terminal m is connected to the electro-
magnet L, the alarm apparatus i, and through this to the clockwork u, the
minimum terminal n is connected through the resistance s to the alarm i, and the
clockwork . The operation of the apparatus is as follows:-
The agitator and the air supply are first set going, then the crushing rollers
are put in operation and the requisite amount of pulverized cork and ochre are
introduced through the hopper C, and finally the requisite quantity of oil is

page_text: added through the cock q¹. At the commencement of the operation the agitator
should revolve about 40 revolutions per minute, which speed is reduced towards
the end of the process. The arms of the agitator turn in the direction of their
non-perforated sides. After this has gone on for some 10 or 15 minutes the
thermostatic regulator begins to act the surface of the mercury in F reaches
the terminal n and a current of electricity flows from p, through n, S, u, and i.
The mixture in operation evolves considerable water vapour during the first stage
of the oxidation; as the oxidation proceeds acid vapours and strongly odorous
gases escape. A portion of these vapours and gases are condensed in the pipe K,
and flow back towards N, through which they are periodically withdrawn.
When the temperature has risen to the requisite degree the electric current will
pass through the electromagnet L; the magnet immediately attracts its arma-
ture causing it to revolve on its axis and thereby to close the valve 3
leaving open the valve c¹. The cold air entering the tube c³ consequently no
longer passes through the heating apparatus but flows directly into the agitator
through the hollow shaft W. When this action takes place the speed of revolu-
tion of the agitator is reduced one half and the requisite quantity of hard resin
ground to a powder and mixed with from 5 to 10 per cent. of carbonate of magnesia
The mixture soon coagulates to
(Magnesite) is added to the half prepared mass.
a viscous mass and lumps are formed causing considerably greater resistance
to the agitator arms and to the blast. The oxidation may require from one to
four hours and may be regarded as complete when the mass still remains plastic
when warm and yet forms a tough and rubber-like lump at ordinary temperatures
and is no longer glutinous. Moreover, the mixture is not liable to spontaneous
decomposition at 70° Centigrade, nor does it exhale any quantity of gas or vapour.
In order to obtain a perfectly dry and non-odorous mass a considerable quantity
of cold air is passed through it for some time. When the operation is completed
the discharge chamber G is opened and the finished product falls into the funnel T
and is passed through a pair of roliers provided with a scraping device and is
then ready to be impressed on the backing in the usual manner.
Dated the 19th day of June 1899.
W. P. THOMPSON & Co.,
322, High Holborn, London, W.C., Patent Agents for the Applicant.
A Process for the Rapid Oxidation of Drying Oils and their Fatty
Acids, by Mixing and Airing the same with Pulverised Sub-
stances for the Preparation of Linoleum and Cork Sheeting.
I, DR. JOSEPH HERTкORN, Chemist, of 29, Kalvinstrasse, Berlin, Germany, 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:
-
The reduction of siccative oils to their rubber-like final products has been the
subject of Patents in Great Britain No. 209 of 1860, No. 2057 of 1871 and No. 2845,
of 1872. The processes set forth in these Patents have aimed at obtaining a
very intimate contact between the oils when mixed with siccative materials, and
the atmospheric air by the aid of increased temperatures. The object in view
has been attempted to be attained either by forcing air through the heated oil or
allowing the latter in a fmely divided condition to pass through heated air;
or the oil has been exposed to the air by pouring it in thin layers on scrim sus-
The viscid or solid mass of oxidized oil
pended or extended in heated rooms.

page_text: thus obtained had then to be subdivided into small pieces by means of rollers or
the like and was then melted with a mixture of soft and hard resins and finally
mixed with ochre and pulverized cork. These processes, however, possess various
disadvantages. For instance, the oxidation of the oil if undertaken separately
as above set forth, involves the use of extensive complicated and costly plant
and the working expenses become very. high, whilst the output is limited and
moreover the product obtained is either too sticky or else insufficiently cohesive,
conditions caused either by overcharging or by incomplete or not uniform oxida-
tion of the mass. Further, the subsequent mixing with the linoleum filling mass
requires a number of expensive machines and the use of a large plant, and even
then the mixture of the ingredients is in many cases only imperfect.
My process is devised to obviate these draw-backs. I have discovered that
this may be obtained by effecting the oxidation of the siccative oils (with or without
the addition of driers) after adinixture thereof with pulverized, bulky, or specifi-
cally light material, through which mixed mass hot air is preferably caused to
pass. A suitable mixture of materials for carrying out my process is the
linoleum filling mass usually employed consisting essentially of pulverized cork
and sawdust. The oxidation of a large quantity of oil can be accomplished in
from one to two hours by this method, whilst by the process usually employed
hitherto days or even months' may be necessary. The linoleum mass obtained
by my process is perfectly inodorous, uniformly mixed, oxidized throughout and
highly elastic. The mixture of glutinous matter of substances with the filling
mass is practically perfect. I may add certain hard resins in a finely pulverized
or ground condition to the half oxidized mass to increase its cohesive and elastic
qualities. To prevent the spontaneous ignition of the linoleum mass, saturated
with oil as described, I mix with it earthy alkaline oxides or compounds thereof,
or earthly alkaline soaps. Those ingredients produce in the linoleum a certain
hardness and velvet-like smoothness, together with leather-like flexibility and
superior tenacity. In order more clearly, to st forth my invention, I have
illustrated in the drawing accompanying the Provisional Specification diagram-
matically and in plan view one method of constructing a plant suitable for the carry-
ing out of my invention. The operation is preferably conducted as follows:-
:-
The usual amount of colophony as well as a quantity of resinate of magnesia
is melted with the linseed oil which is boiled together with drying materials,
and the mixture is then whilst still in the hot state pumped into the reservoir Q.
A usual charge is 500 to 600 kilos. and is composed of say: linseed oil about
200 kilos., rosin 14 to 17 kilos., Kauri gum 8 to 20 kilos., resinate
of magnesia 20 to 40 kilos., cork meal 230 to 236 kilos., ochre 120
to 125 kilos. The contents of this reservoir are gradually heated to about
70° C. The reservoir is provided with draw-off cocks q, q², q³ in its sides so placed
as each to draw off a quantity of about 100 kilogrammes. The said cocks are
connected with the supply pipes R, R', the former of which pipes is enclosed in
the mixing cylinder or apparatus A and perforated as shewn. The said mixing
cylinder A is preferably a horizontal cylinder constructed of boiler plate and
bedded on a cast-iron frame suitably placed near the mixing rollers. The upper
part of A is provided with a manhole and also with a hopper C; the said man-
hole is provided with a valve or damper Sand the hopper is
provided with a cover M so that by means of these the cylinder A may
be shut off from the outside. The cylinder A is further provided with the funnel
or pipe B having a damper or valve S and into which a pipe K projects. This
pipe K serves to heat the oil. I further provide a receptacle for the condensed
water and a sluice N. The bottom of the cylinder A. is provided with a discharge
door G supported on suitable guide rollers along its entire length, and so arranged
as to allow the mixed mass to fall into the iron funnel T when required, and
from thence to the mixing rollers.
The mixing vessel A is provided, moreover, with an agitator constructed as
follows:-

page_text: The hollow shaft W passes axially through the apparatus and has attached
it hollow wings W, W, W3, W+, and so forth, bored out on one side. These
ings are placed alternately in opposite directions at an angle of 25° to the
id shaft. At one end of the said shaft W is a belt pulley E which can be
riven at the required speed from a prime mover of any kind. The other end
the shaft W terminates in a stuffing box D to which is likewise connected the
ir pipe c, and the carbonic acid gas receptacle c. Through the air tube c³
ompressed air is driven, and may, if required, be supplied heated to 70°
Centigrade. For this purpose there is provided a heating apparatus, such for
nstance as that indicated in the diagram at H through which the air is forced
rom an outside source of supply, through, then through the heating apparatus H
nd back to the agitator through the lower pipe in the direction indicated by
he arrow.
The heating apparatus shewn is intended to be heated by steam
bassing through the coil or serpentine pipe indicated, to a steam trap on the
outside of the apparatus. Suitable valves care provided in the forked pipe
for the regulation of the supply of air and its temperature, and are automatically
The steam heating device H is preferably
controlled by the thermostat.
The electrical heat
heated by steam at from 7 to 10 atmospheres' pressure.
regulator is constructed as follows:-
Frepresents a tube containing a mercury column having a bulb at its lower
end and an expanded container at the top. The barometer tube F passes into
the interior of the agitator W and its expanded top projects above the same;
this part is calibrated and graduated and within it are suitably placed the ter-
The maximum terminal m is
minals m, n, and the lowermost connection p.
connected to the electromagnet L, the alarm apparatus , and through this to the
clockwork u the minimum terminal n is connected through the resistance s to
The operation of the apparatus is as follows:--
the alarm i, and the clockwork u.
The agitator and the air supply are first set going, then the crushing rollers
are put in operation and the requisite amount of pulverized cork and ochre are
introduced through the hopper C, and finally the requisite quantity of oil is
added through the cock q¹. At the commencement of the operation the agitator
should revolve about 40 revolutions per minute, which speed is reduced towards
the end of the process. The arms of the agitator turn in the direction of their
After this has gone on for some ten or fifteen minutes the
non-perforated sides.
thermostatic regulator begins to act the surface of the mercury in F reaches
the terminal n and a current of electricity flows from p, through n, S, u, and i.
The mixture in operation evolves considerable water vapour during the first stage
of the oxidation; as the oxidation proceeds acid vapours and strongly odorous
gases escape. A portion of these vapours and gases are condensed in the pipe K,
and flow back towards N, through which they are periodically withdrawn.
When the temperature has risen to the requisite degree the electric current will
pass through the electromagnet L; the magnet immediately attracts its armature
V causing it to revolve on its axis about 90° and thereby to close the valve c²
The cold air entering the tube c³ consequently no
leaving open the valve cl
5 longer passes through the heating apparatus but flows directly into the agitator
through the hollow shaft W. When this action takes place the speed of revolu-
half and about
tion of the agitator is reduced
resin land to 10 kilos. Kauri gum per 100 kilos. of oil used preferably also
mixed with from 5 to 10 per cent. of carbonate of magnesia: (magnesite) are
The mixture soon coagulates to a viscous
50 added to the half prepared mass.
mass and lumps are formed causing considerably greater resistance
the agitator arms and to the blast. The oxidation may require from one to
four hours and may be regarded as complete when the mass still remains plastic
when warm and yet forms a tough and rubber-like lump at ordinary temperatures
55 and is no longer glutinous. Moreover, the mixture is not liable to spontaneous
gas or vapour
decomposition at 70° Centigrade, nor does it exhale any quantity
In order to obtain a perfectly dry and non-odorous mass a considerable quantity
one
to 15 kilos.
to

page_text: of cold air is passed through it for some time. When the operation is completed
the discharge chamber G is opened and the finished product falls into the funnel T
and is passed through a pair of rollers provided with a scraping device and is
then ready to be impressed on the backing in the usual manner.
My invention is not limited to the proportions given above, which are cited by
way of example, because the various qualities of linoleum, and the different pur-
poses to which the article is applied, require variations in the ingredients, as is
well known to those skilled in the art.
Thus for instance ground cork may be replaced wholly or partially by saw dust,
about in the proportion of 200 kilos. of the latter to 235 kilos of the former, or
the quantity of ochre given may be reduced by about one-half according to the
kind employed, and so forth.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is:-
1. In the manufacture of linoleum and the like, the process for oxidising drying
oils and their fatty acids consisting in boiling the oil with or without oxidising
agents and earthy alkaline compounds or mixtures of these bodies, and subse-
quently mixing the resultant mass with other materials and supplying air or
oxygen during the process in a mixing cylinder, all substantially as set forth.
2. The improved apparatus for mixing and aerating the compound set forth in
Claim 1 by means of which hot or cold air is automatically supplied through
the hollow shaft W and the hollow and perforated wings such as W₁, substantially
as and for the purposes set forth.
Dated this 21st day of June 1899.