The Manufacture and Production of Hydrocarbon Products or Compositions for use for Insulating or other Purposes.
Year: 1891

page_text: Date of Application, 19th May, 1891-Accepted, 20th June, 1891
COMPLETE SPECIFICATION.
The Manufacture and Production of Hydrocarbon Products or
Compositions for use for Insulating or other Purposes.
1, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by John Weir of New York City in the
County and State of New York United States of America and in what manner
the same is to be performed to be particularly described and ascertained in and
by the following statement:-
The hydro-carbon product in which the present invention is mainly comprised
is a resinoid hydro-carbon termed by my foreign correspondent "litho-carbon."
Its chemical constitution is.
Carbon
Hydrogen
Oxygen
Sulphur
88.23
11.59
.06
trace
Litho-carbon is a solid product devoid of viscousness, of a jet black colour,
flexible and somewhat plastic at ordinary temperature, of high gloss and of great
toughness; in flexibility and toughness it indeed resembles india rubber, but is not
elastic to the same degree. Its specific gravity is about 1028, that is to say
from 1-000 to 1.028. It fractures only at low temperatures, when it will show a
slight conchoidal fracture. It is soluble in naphtha, benzole, chloroform, bi-sulphide
of carbon and partially soluble in ether, completely in turpentine, rosin oils, and
the like. It is not sensitive to sunlight. It will stand a temperature of 600 degrees
Fahrenheit without giving off dissociated products. It resists alkalies and acids
except concentrated nitric and concentrated sulphuric acids. It amalgamates
perfectly with rubber; and shews signs of vulcanisation when in combination with
rubber.
Thus in very many of its physical characteristics (particularly those which
invest it with its peculiar value for industrial uses) it is essentially different and
distinguishable from asphaltum, maltha or bitumen.
Litho-carbon differs from the substances just named not only in the respects last
noted, but in chemical constitution as well. So far as my foreign correspondent
has been able to determine, it is not to be classed with such bodies as asphalts, and
the like, nor does it belong to the olefine or paraffine series to which the latter
belong. From the analysis above stated it is manifest that litho-carbon has the
formula CH which is the one for all terpenes; and, so as can be determined it
appears to be one of the higher polymeric members of the terpene series.
10 16
Litho carbon is obtained according to this invention by the suitable treatment of
a natural substance which is found in large quantities in the State of Texas in the
United States of America, this substance being a hydrocarbon material contained
in or combined with sand or shell rock.
This material separated from the lime or sand rock, and in its natural state,
analyzes as follows.
1
05.10

page_text: differences between the two, particularly as to the sulphur and oxygen constituents.
The natural substance has no oxygen practically, and a noticeable percentage of
sulphur. Were these characteristics in the litho-carbon, they would injuriously
affect it. The absence of oxygen would take from the litho-carbon its toughness
and elasticity the presence of sulphur would unfit the litho-carbon for use, for
example, in paints owing to its liability under these circumstances to evolve
sulphuretted gases, thus causing spongy porous films and blisters.
The natural substance moreover taken from the sand or shell rock is not a solid
but is a semi-liquid, highly sticky, dark brown or black, product, which does not
solidify but is permanently viscous and has no drying qualities whatever. This
latter objectionable characteristic, is due to the fact that one of the constituents of
the natural substance, is a volatile oil which amounts to from to 1 per cent. of the,
said natural substance.
In order to obtain litho-carbon from this crude material there is employed
according to this invention a process which involves three steps, riz.: first, separating
the crude hydrocarbon from the sand or shell rock by means of a solvent, secondly
evaporating or driving off the solvent, and thirdly treating the remaining hydro-
carbon with steam or hot air or both, whereby the volatile constituent and the
sulphur hereinbefore referred to are driven off, and the hydrocarbon is caused to
absorb the needed proportion of oxygen.
In this process
may use any suitable solvents such as petroleum-naphtha,
benzole, bisulphide carbon, turpentine, or the like. I prefer petroleum-naphtha
owing to its cheapness and to the ease with which it can be recovered without
considerable loss.
The following is a description of an apparatus suitable for carrying out the
process reference being had to the accompanying drawing which represents in side
sectional elevation so much of said apparatus as is required for an understanding of
the manner in which the process may be carried out.
It will of course be understood that this apparatus is merely typical of a variety
of appliances which might be used, and that I do not limit myself to any particular
construction of apparatus shewn.
A is a tank for holding the solvent, B is a vessel for holding the rock or natural
substance aforesaid reduced to fragments of any desired size.
The vessel B has a perforated false bottom a. E represents a vessel containing
a condensing coil.
is the vapour pipe, conducting the solvent in the form of vapour to the contents
of the vessel B.
c is a trap pipe, conveying the extract to the bottom of the tank A.
C is a steam jacket around the tank A with a steam inlet i and outlet k for steam
and water of condensation. d is exit vapour pipe leading to the condenser, E,
opened when solvent is to be distilled off from the extracted hydrocarbon in the
tank A. e is a vapour pipe to be opened after extraction when live steam is
introduced into the vessel B through the perforated pipe g carrying steam and last
traces of naphtha held in the rock to the condenser E. is a steam pipe running
along the bottom of the tank A where it is perforated, his outlet valve for the
finished artificial product, which can thence be drawn in a molten state into suitable
receptacles.
t
All of the pipes are of course provided with suitable cocks as indicated.
The operation of extraction is as follows. The tank A receives the solvent
(which may conveniently be naphtha) while the vessel B is filled with the ground
or crushed rock resting on the perforated bottom a
Steam is turned on in the steam jacket C causing the naphtha in the tank A to
boil and send its vapours through the pipe into the vessel B, where the said
vapours condense in the fragments of rock and exert the dissolving effect on the
said rock eliminating or carrying down in solution the native hydrocarbon through
the pipe c to the bottom of the tank A. During this time the condenser E is shut off
from the tank A. and vessel B. After extraction is complete, that is when the liquor

page_text: running from the tube c is almost colourless or is but naphtha the cocks of the
pipes and c are shut and the tank A is then connected with the condenser E
through the pipe d and the said condenser is put in communication with the
vessel B through pipe e. The steam heat in the jacket C then causes the naphtha
to distil off from the litho-carbon hydrocarbon the said naphtha being recovered by
passing into and being condensed in the coil of the condenser E.
At the same time steam is turned into the vessel B by the perforated pipe g,
whereby all the adhering naphtha is driven off from the rock and is passed into
and condensed in the condenser E, the naphtha there rising to the top of the
condensed water.
When the naphtha has stopped running from the tank A dry steam or hot air is
introduced through the perforated pipe, and rises through the heated and still
molten litho-carbon carrying with it the last traces of naphtha, and a volatile oil of
specific gravity 835. This oil carries with it most of the sulphur contained in the
native substance, while small quantities of sulphur are also visible in the milky
water condensing in E.
As soon as the steam or hot air ceases to carry over any more of this volatile oil
(the quantity of which is usually from to 1 per cent. of the native product) and
the condensing water is clear the supply of steam by the pipe is stopped and the
hydrocarbon product (litho-carbon) which has thus been produced is allowed to run
into suitable receptacles where it can solidify.
An absorption of oxygen takes place while eliminating the volatile oil, especially
at the last stage of running open steam or a current of hot air into and through the
heated litho-carbon. It is to this action that the proportion of oxygen above
shewn to be present in the litho-carbon is due. The temperature of the hot air
should be somewhat higher than that of the molten litho-carbon.
This product (litho-carbon) is one capable of extensive and varied uses-for
instance it may be used for insulating purposes; as a substitute for rubber or gutta
percha or for amalgamation with the same; for waterproofing textile fabrics,
leather, wood fibre and the like; in the manufacture of paints, varnishes and
japans as a lining for casks, barrels and other hollow bodies, such for example as
tanks for holding acids; or it may be used in making paving compositions and
building material, and in sheet form as roofing material, in which case it can be
overlaid on one or both faces with paper or textile fabric as now customary in the
use of plastics for roofing or it may be used as a saturant or coating for bricks and
the like; or as a coating for leather to produce what is known as "patent
leather or as a strengthening and waterproofing substance for machine belting or
hydraulic hose of fabric or other material; and generally it may be used in any
connection where an insulating, waterproof, or acid proof, material is required,
either alone or in combination with other ingredients.
E
"
For use as a paint, the litho-carbon is incorporated with a solvent and a suitable
pigment or pigments-the litho-carbon being brought to a molten condition, and in
such condition being mixed with a suitable solvent such as spirits of turpentine
which preferably is preliminarily heated to near its boiling point. The proportion
of solvent to litho-carbon will vary with the desired consistency of the paint; in
general the litho-carbon may be from one fourth to equal volume as compared with
the solvent. The colour of the paint can be varied by pigments-which (of
whatever colour or character desired) are added to the mass and thoroughly
incorporated therewith which may be done by grinding in the usual way. The
pigments may be white lead, zinc, ground asbestos, talc, infusorial earth, oxide of
iron, vermilion, chrome green, ultramarine or the like. From 2 to 12 pounds of
pigment to each gallon of the solution may be advantageously employed. Boiled
linseed oil may be added if desired, as may also drying agents such as borate of
manganese, red lead and the like. This paint is strongly adhesive to wood or
metal, gives an enamel like surface resists dilute acids and alkalies and will
withstand without deterioration or change a temperature of 400 degrees Fahrenheit
and upwards.

page_text: In the preparation of varnish or japan the litho-carbon is brought to a semi-fluid
condition by heat and is then incorporated with a suitable solvent such as spirits of
turpentine, benzole, toluole, xylole, bisulphide of carbon, petrobenzine, refined
petroleum, or mixtures of them-the proportion of solvent to the litho carbon
depending upon the fluidity which it is desired to impart to the varnish or japan.
Additional hardness and glass-like finish may be obtained by incorporating with
the varnish or japan (during the process of making it) a gum resin, such for
example as gun copal.
As above indicated the litho-carbon will amalgamate with india-rubber and the
like. Such a compound is useful for many purposes such for instance as for the
production of sheets or tissues suitable for the production of waterproof fabrics for
macintoshes and other articles of clothing.. For this purpose the litho-carbon may
be combined with any desired quantity of india rubber, gutta percha or oxidized
linseed oil in proportions of from say 5 to 50 per cent. of the whole mass. Good
results can be obtained with from 85 to 80 parts of litho-carbon combined with
from 15 to 20 parts of india rubber gutta percha or oxidized linseed oil. The
litho-carbon and rubber may be amalgamated by being passed together through
machinery such as is now employed for working rubber; or any other suitable
means of combining the two may be employed, as for instance for melting the
litho-carbon and dissolving in it the desired proportion of rubber.
The compound thus produced is passed in solid form between calendar rolls
such as used in rolling rubber or plastic material and is thus reduced to sheet form.
A good insulating compound for electrical purposes can be obtained by combining
litho-carbon with sulphur--or with sulphur and india rubber, gutta percha or linseed
oil. The litho-carbon may be incorporated with the sulphur when the litho-carbon
is in a molten condition and in a suitable receptacle and subjected to a heat of say
from 250 degrees to 325 degrees Fahrenheit for say an hour more or less-the resultant
product being a compound which is an electrical insulator equal to vulcanized
rubber. The same process can be employed when rubber, gutta percha or linseed
oil is employed in addition to the sulphur. The proportion of sulphur when used
alone with the litho-carbon may be say 5 parts to 55 parts by weight of litho-carbon.
When india rubber or the like is used in addition, the sulphur may be from 2 to
25 per cent., and the india rubber or the like from 5 to 50 per cent., of the whole
mass.
A more perfect insulator and one which is effective as a substitute for gutta
percha for submarine insulation may be obtained by incorporating together in a
homogeneous mass litho-carbon, gutta percha and gum shellac (to which latter may
be added if desired gum dammar or gum copal).
These ingredients can be melted together and thoroughly mixed and amalgamated
by careful stirring; or they can be combined in any other suitable way. They can'
be combined in varying proportions, proportions which give excellent results are
litho-carbon 65 parts, gutta percha 25 parts, gum shellac 10 parts all by weight.
The composition thus obtained is very tough, has a somewhat higher melting point
than gutta percha, is an absolute non-conductor of electricity and is a non-absorbent
of water, and remains non-porous and unchanged at a heat of even 300 degrees
Fahrenheit. Wires and electrical conductors can be covered with this com-
position in the same way and by the same means as those now employed to coat
conductors with gutta percha.
Litho-carbon however even alone is an efficient electrical non-conductor; and it'
can be advantageously used for this purpose by being combined with paper or wood
pulp or other fibrous material, such, for example, as papier maché, asbestos,
mineral-wool or equivalent fibrous or absorbent material, and it may thus be
combined with, the pulp, papier maché or fibrous material either before, or after, the.
latter is moulded or shaped into definite form-the combining of the formed article
with the litho-carbon being effected by immersing the article in molten or liquid
litho-carbon until the desired degree of saturation has been attained, and by..
subsequently exposing the article (to obtain the best results) for some minutes to a

page_text: temperature of 220 degrees Fahrenheit or upwards to insure the uniform and
thorough penetration and impregnation of the material by the litho-carbon.
If it be desired to mix together the fibre or pulp and the litho-carbon, before the
fibrous material is put into shape, this can be effected by heating the litho-carbon
(with or without a solvent) to bring it to molten condition and then adding to it
pulp or fibrous material in proper proportion say from 20 to 25 parts by weight of
litho-carbon to from 25 to 80 parts by weight of wood pulp, or the like. The
composition thus obtained of course hardens by cooling.
The composition will be found to be hard, tough, somewhat clastic, very firm and
strong, having many of the properties, of, and closely resembling in appearance,
vulcanite or hard rubber.
In some instances--as for example in making the hard rubber substitute it is
preferred to more highly oxidize the litho-carbon prior to its mixture with the
fibrous body. This can be effected by melting the litho-carbon in a steam heated
vessel, and blowing air through it until the desired degree of oxidation is reached;
and to facilitate the oxidizing action some agent such as powdered oxide of
manganese or litharge for example can be added to the molten mass.
This agent
will finally settle and can be strained or otherwise removed.
The composition of fibrous material or pulp and litho-carbon-whether the fibrous
material or pulp be moulded into form before or after it is combined with the litho-
carbon is useful not only as an insulator or a substitute for hard rubber, but also
for the manufacture or production of water pipes, toys, card board or other articles
and generally for the manufacture of articles heretofore made of papier maché or
other plastic compositions.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed 1 declare that what
I claim is.
First. The new hydro-carbon product termed "litho-carbon "having the attributes
and characteristics hereinbefore specified.
Second. The manufacture of litho-carbon" consisting in separating the crude
natural substance from the sand or other mineral by means of a solvent, separating
or driving off the solvent from the crude material thus obtained; and injecting
steam or hot air into the said crude material in order to drive off the sulphur and
volatile oil constituents of the material and to supply the residue with oxygen as
herein before set forth.
"
Third. The combination of the above described "litho-carbon with ingredients
such as are hereinbefore specified for the production of compositions of matter for
insulating and other purposes, substantially as hereinbefore set forth.
Dated the 10th day of May 1891
J. H. JOHNSON & Co.