Improvements in the Manufacture and Application of Terebenthene Monohydrochloride.
Year: 1896

page_text: Date of Application, 22nd Sept., 1896
Complete Specification Left, 17th June, 1897-Accepted, 18th Sept., 1897
Improvements in the Manufacture and Application of Terebenthene
Monohydrochloride.
I, JOHN GEDDES MCINTOSH, of 9 Parsonage Street, Cubitt Town, London, E., do
hereby declare the nature of this invention to be as follows:-
My invention relates to improvements in the manufacture of terebenthene
monohydrochloride and in the application of same in the production of celluloid and
other materials.
Terebenthene monohydrochloride is prepared as is well known by subjecting spirits
of turpentine to the action of hydrochloric acid gas which converts the turpentine into
a mixture of crystallisable and liquid monohydrochloride (CIHHCI) the crystallis-
able portion being subsequently treated in different ways to obtain the desired
crystals..
None of the processes however at present known to me are sufficiently perfect when
carried out on a large scale and are therefore, unsatisfactory from a commercial point
of view.
In carrying out my invention I pass a current of dry hydrochloric acid
gas through
spirits of turpentine (preferably American) maintained at a regulated temperature by
a worm or other means. The resulting product being a mixture of the crystalline
and liquid monohydrochloride, is then mixed with a solution of caustic alkali such as
caustic soda, potash, or ammonia, and distilled.
After drawing off the water from the distillate the latter is washed with water
several times if required to free it from adventitious products and the liquid
monohydrochloride is then separated from the crystalline and crystallizable portion
by filtration in a vessel surrounded by a cooling mixture or otherwise suitably cooled
so that the liquid may readily leave the cooled crystallized portion and be collected in
a separate vessel.
When all the liquid portion has been drawn off the crystallized portion is pressed to
separate the last traces of the liquid monohydrochloride and the former is ready for
use or for recrystallization if desired.
In order to prevent a draw-back from the receptacle containing the spirits of
turpentine into the vessel in which the hydrochloric acid gas is generated, the gas is
first passed into a closed vessel containing a small quantity of sulphuric acid at the
bottom.
The gas inlet and exit pipes connected to this vessel enter same but without
dipping into the sulphuric acid while a pipe open to the air passes directly into the
acid so that when from any cause gas ceases to flow equilibrium is established by
air drawn in through this pipe and passing through the acid.
In the manufacture of celluloid and products thereof, such as the material-known as
"Pegamoid" as well as in the manufacture of soaps, deodorizers and embrocations
and other materials I propose to employ the distilled product obtained as above

page_text: either in its liquid or crystallized or finished form or a mixture of both or all of these
as a substitute for the crystallized natural camphor at present employed the liquid
acting as a solvent.
COMPLETE SPECIFICATION.
Improvements in the Manufacture and Application of Terebenthene
Monohydrochloride.
I, JOHN GEDDES MCINTOSH, of 9 Parsonage Street, Cubitt Town, London, E.,
Analytical and Consulting Chemist, 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:-
My invention relates to improvements in the manufacture of terebenthene mono-
hydrochloride, solid and liquid, so as to obtain final products, better adapted as a
substitute for natural camphor, or per se in the production of celluloid and other
materials.
Terebenthene monohydrochloride is prepared as is well known by subjecting spirits
of turpentine to the action of hydrochloric acid gas which converts the spirits of
turpentine into a mixture of crystalline and liquid monohydrochloride (CHHCI).
None of the processes however at present known to me are sufficiently perfect when
carried out on a large scale, as they do not yield final products, refined enough for
use in the arts, in a cheap and efficient manner, and are therefore unsatisfactory from
a commercial point of view.
In carrying out my invention I pass a current of dry hydrochloric acid gas through
spirits of turpentine (preferably American), or its isomers maintained at a
temperature of about 140° F. to 180° F. by means of hot and cold worms or in
other ways.
In order to prevent a drawback from the receptacles containing the spirits of
turpentine into the vessel in which the hydrochloric acid gas is generated the
hydrochloric acid gas is first passed into a closed vessel containing a quantity of
sulphuric acid.
The hydrochloric acid gas inlet and exit pipes connected to this vessel enter the
same but without dipping into the sulphuric acid, while a pipe open to the air passes
directly into the sulphuric acid so that if from any cause hydrochloric acid gas ceases
to flow equilibrium is established by air drawn in through this vessel and passing
through the sulphuric acid.
The hydrochloric acid gas from this vessel is then led by means of a tube to the
bottom of the vessel containing the spirits of turpentine, the portion of the tube
resting on the bottom being preferably coiled and perforated so that a more thorough
commingling of the hydrochloric acid gas with the spirits of turpentine may be
obtained. Any unabsorbed hydrochloric acid gas passing out of the vessel, as well as
any vapour from the spirits of turpentine, or the converted portions thereof, is led
into a similar vessel also charged with spirits of turpentine kept at the same temperature

page_text: as in the preceding vessel, and if need be into further vessels similarly charged and
regulated, until all the hydrochloric acid gas is spent.
The whole process is continued until the spirits of turpentine contained in the first
vessel is saturated and so on in each succeeding vessel in rotation, the necessary
separations from and adjustments to the generating vessel being also effected in
rotation.
The collected saturated products being a mixture of the crystalline and liquid
terebenthene monohydrochloride is then mixed with a solution of caustic alkali, such
as caustic soda, caustic potash, or liquor ammonia and distilled, the alkaline solutions
being made so dilute that the water in which the alkalies are dissolved generates a
current of steam which passes over and condenses with the refined monohydrochlorides
during the whole course of the operation.
This conjoint distillation of the liquid and solid monohydrochloride greatly prevents
the choking up of the exit and condensing pipes from the still which takes place
when the solid monohydrochloride is distilled after separation from the liquid, an
advantage further intensified by the simultaneous passing of steam from the alkaline
solutions. Should these from any cause become so concentrated that the steam is
not generated, the still may be allowed to cool and sufficient water added to cause
steam to again pass over with the distillates.
The distillates are collected in a large glass or porcelain vessel containing cold
water. After drawing off the water from the distillates, they are washed with water
several times to free them from adventitious products if need be, and the liquid
monohydrochloride is then separated from the crystalline by filtration in a vessel
surrounded by a cooling mixture and is collected in a separate vessel. But the greater
part of the solid may if the weather be not too warm separated by passing the
distillate into long narrow calico or suitable filter bags suspended from the ceiling or
any convenient point, and the liquid may then be further filtered through the vessel
surrounded by a cooling mixture referred to above.
When the liquid portion has been separated from the crystalline portion in the
manner described, or by passing it through a centrifugal machine, the crystalline
portion is pressed to free it from the last traces of the liquid monohydrochloride.
In the manufacture of celluloid and products thereof such as the material known
as "Pegamoid" as well as in the manufacture of soaps, varnishes, antiseptics,
insecticides, perfumes, embrocations, and other materials, I propose to employ the
distilled products obtained by the process described as above either in their liquid or
crystalline state or a mixture of any or all of these as a substitute for crystalline
natural camphor, or oil of camphor, eucalyptus oil, or thymnol, or such like at present
employed.
As antiseptics, I find that they are per se more valuable than natural camphor,
eucalyptus oil and such like.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what I
claim is :-
1. In the manufacture of commercial terebenthene monohydrochloride the
distillation together of the crude crystalline and liquid terebenthene monohydrochloride
substantially as described.
2. In the manufacture of commercial terebenthene monohydrochloride the
distillation of the crude crystalline and liquid terebenthene monohydrochloride with
a solution of caustic alkali, substantially as described.
3. The treatment of the combined distillates by filtration and cooling to separate
the solid from the liquid terebenthene monohydrochloride, substantially as
described.
4. The employment of the liquid or crystalline terebenthene monohydrochloride
or a mixture of same as a substitute for crystalline natural camphor or the like in
the manufacture of celluloid and products therefrom and in the manufacture of soaps,
antiseptics, and the like, substantially as described.

page_text: 5. The improvement in the manufacture of commercial
monohydrochloride, substantially as described.
Dated this 17th day of June 1897.
terebenthene
For the Applicant.
PHILIP M. JUSTICE,
55 and 56 Chancery Lane, London, Chartered Patent Agent.