Improvements in or relating to the Manufacture of Camphors or Isomers thereof.
Year: 1896

page_text: Date of Application, 17th Feb., 1896
Complete Specification Left, 17th Dec., 1896-Accepted, 23rd Jan., 1897
PROVISIONAL SPECIFICATION.
Improvements in or relating to the Manufacture of Camphors
or Isomers thereof.
I, JAMES CHARLES RICHARDSON, of 19 Claremont Square, in the County of
London, N., Electrochemical Engineer, do hereby declare the nature of this invention
to be as follows:-
These improvements relate to the manufacture of camphors and essential oils,
directly or indirectly, from such bases as turpentines, and the like, especially with a
view to the making of compounds free from acid re-action at normal or elevated
temperatures.
According to this invention a better class of compounds is produced than
hitherto.
Briefly stated, I treat turpentine, or isomerides thereof, or compounds approxi-
mating thereto, hydrochlorides thereof, artificial camphor,' so-called, or like
compounds, electro-chemically, or with such materials as sodium dioxide, barium
dioxide, sodium or alloys thereof, with water or steam or water-gas,' or like
specifically positive elements or compounds as aluminium or zinc oxide or magnesia,
or with ozone or electrically-charged oxygen or other gas or gases, hydrogen
dioxide or its equivalent, carbon monoxide or dioxide gas, liquid, or solution,
ammonia or its compounds, or like metallic or non-metallic carbonyls, carbonates,
oxides, hydroxides, hydrides, halogen compounds, sulphides or the like, or oxygen-
carrying salts, as chlorates, manganates, or acids, alkalis, carbon or hydrocarbon
compounds.
The turpentine or its equivalent, or the hydrochlorides or the like, may be treated
as solids, in solution, liquid, vapour or gas, the same may be rendered acid, alkaline
or normal, of any density and at any temperature (I may employ artificial cooling
agents) and pressure.
The raw products may be purified or finished by washing, distillation, precipitation,
sublimation, or other means, and moulded by pressure, or other means, into blocks
for the market. The mother liquor or liquors, and other by-products, I utilise in
various ways, which reduces cost of manufacture.
To be more precise as to the nature of this invention, I give the following
examples:
1. I treat turpentine in lead, or lead-lined chambers, or slate or stoneware or other
suitable tanks with peroxide of sodiuin and an acid such as hydrochloric acid by
which peroxide of hydrogen is produced. This peroxide of hydrogen oxidises the
turpentine into the condition of camphor, or isomers thereof, according to the
equation expressed by the empirical formula-C10H16 + H₂O₂ = C10H10 + H₂O.
The peroxide and the turpentine may be filtered through sand or other material
corresponding to capillaries to effect a more rapid action, or the same may be
effected by pressure. But the temperature must be kept down or higher oxidation
products are obtained, and this I effect by cooling agents such as water or other
convenient agent.
2. I treat turpentine hydrochloride with peroxide of sodium, which removes the
acid therefrom according to the equation 2 C₁HCl + Na2O2 = 2 C10H170 + 2 NaCl.
In this way I get rid of the hydrochloric acid by the formation of common salt, at
the same time tacking on oxygen to the turpentine molecule.
Dated this 17th day of February 1806
JAMES C. RICHARDSON.

page_text: COMPLETE SPECIFICATION.
Improvements in or relating to the Manufacture of Camphors or
Isomers thereof.
1, JAMES CHARLES RICHARDSON of 19 Claremont Square, in the County of
London, N., Electrochemical Engineer, 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 :-
These improvements relate to the manufacture of camphors and essential oils
directly or indirectly from such bases as turpentines, and the like, especially with a
view to the making of compounds free from acid re-action at normal or elevated
temperatures.
According to this invention a better class of compounds is produced than
hitherto.
I treat turpentine, or isomerides thereof, or compounds approximating thereto,
hydrochlorides thereof, artificial camphor,' so-called, or like compounds, electro-
chemically, or with such materials as sodium dioxide, barium dioxide, sodium or
alloys thereof, with water or steam or water-gas, or like specifically-positive
elements or compounds as aluminium or zinc oxide or magnesia, or with ozone or
electrically-charged oxygen or other gas or gases, hydrogen dioxide or its equivalent,
carbon monoxide or di-oxide gas, liquid or solution, ammonia or its compounds, or
like metallic or non-metallic carbonyls, carbonates, oxides, hydroxides, hydrides,
halogen compounds, sulphides, or the like, or oxygen-carrying salts as chlorates,
manganates or acids, alkalis, carbon, or hydrocarbon compounds.
The turpentine or its equivalent, or the hydrochlorides, or the like, may be treated
as solids, in solution. liquid, vapour or gas, the same may be rendered acid, alkaline
or normal, of any density and at any temperature (I may employ artificial cooling
agents) and pressure.
The raw products may be purified or finished by washing, distillation, precipitation,
sublimation and moulded by pressure or melting or other means into blocks for
the market. The mother liquor and other by-products I utilise as stated farther on,
to reduce cost of manufacture.
To produce oxygen compounds of turpentine I treat that oil in any vessel of inert
material as stoneware, with peroxide of sodium and an acid such as hydrochloric, by
which peroxide of hydrogen is produced. The acid is slightly in excess of the
peroxide added. The resulting oxidised oil may be distilled in the usual way, and
utilised for purposes to which oxidised terpenes are applied.
In treating turpentine hydrochloride direct with peroxide of sodium, I find it
advisable to carry out the reaction in the presence of steam, in any vessel of inert
material as enamelled-iron, stoneware or the like. The proportion of peroxide
added is about sufficient to take up the chlorine as common salt. At the same time
as injecting steam, air may be added, which assists oxidation of the base.
I now proceed to describe some methods I employ in carrying out this invention:
I take turpentine hydrochloride and treat it with alkalis or alkaline earths in or
about the proportions required by theory to neutralise the chlorine, but preferably
in excess.
For example in dealing with artificial camphor,' the chlorine of that compound
is taken up by the alkali base and the camphene or its isomer liberated is oxidised
by air or oxygen to oxy-camphor. In this process I find it advantageous to heat
the air or oxygen to at least the temperature of the vapour of camphene before
meeting it, so as to keep the compound open and more or less dissociated, and
therefore open to attack, ionised.
If the reducing base be a peroxide, such as previously indicated (peroxide of

page_text: sodium) the oxygen is supplied in the re-action. These methods it will be obvious
may be carried out in any vessel or chamber of inert material. Cast-iron enamelled
inside, or lined with thin Doulton tiles I find suitable.
In distilling or subliming the artificial camphor after the manner explained in the
Specification of the British Letters Patent granted to me, dated Oct. 1, 1895,
No. 18,297, the heat of the receiver is maintained so that the distillate is carried into
contact with the reducing agent and the oxidised product condensed in the
usual way.
As an example of how this is done I sublime or distil the artificial camphor and
carry the sublimate through a retort (of iron lined with inert material) charged with
alkali or peroxide of any of the alkaline earths (lime, baryta, magnesia alumina)
or a manganate or permanganate. This retort is set in a furnace nearly vertically, so
that the contents can be heated, at the same time air, which may be previously
heated, is at the same time passed through or into it. The sublimate meeting with the
reducing and oxidising agent undergoes change from a chlorine to an oxygen
compound, which I condense in a separate chamber in the usual way. Fresh alkali
is added to make up for loss by neutralisation, and the neutral product removed from
time to time. Where manganese is added it may be reoxidised by a current of steam
and air as now well-understood, and so act as an oxygen carrier. Sometimes I
place in the retort, coke or other inert material to give a large surface to the
neutralising base, and so make it act as a 'scrubber.' But I wish to state clearly,
that by adding an alkali to the melted turpentine hydrochloride, the chlorine compound
is neutralised. I find that when sodium carbonate, or ammonium carbonate, is added
to melted turpentine hydrochloride effervescence ensues.
In adding ammonium carbonate very complex bodies are produced. I therefore,
for the present purpose, at least avoid nitrogen compounds, as giving rise to nitrogen
derivatives not required; but the same have some useful applications.
In treating the purified hydrochloride, I add to it in or about the proportions
required theoretically, but preferably in excess, the reducing agent direct to the
melted mass (or previously intimately mixed with it)-the heat set up being
sufficient to sublime a portion of it. At the same time hot air is introduced, with or
without the addition of steam, but preferably with steain, to effect oxidation of the
liberated compound. In this case manganese or a peroxide may be added with
advantage as an oxygen carrier.
In treating turpentine direct with oxides, peroxides and tetroxides of the alkalis
or alkaline earths, the proportion of oxidising agent added is sufficient to oxidise all
the available camphene to camphor which, in the commercial article, may yield from
50 to 80 per cent.
The mixture is placed in a closed vessel as in the case of distilling the artificial
camphor, and subjected to a direct current of steam and hot air and the products
condensed in the usual way.
The residual and uncrystallizable camphor oil produced in this manufacture, of
about 955 sp. gr., I utilise as a solvent for gums, resins and such like, as a
vulcaniser for rubber and oxidiser for oils and such like (as for manufacturing
artificial rubber), either alone or mixed with sulphur or sulphur compounds, as in
thickening linseed oil, and as an embrocation either alone or with an emollient
substance. For dissolving gums, I apply the oil direct to the mixed mass to be
dissolved and warm the solution by steam or direct heat allowing any refuse or
insoluble matter to settle out in the usual way, or filter press. I find for certain
natural gums, this solvent possesses advantages over some other solvents.
For vulcanisation purposes I saturate the oil while warm with sulphur, and then
apply the mixture in the usual way.
As an embrocation and for general medicinal purposes I boil the oil with any good
quality of soap until perfectly neutralised. The resulting emulsion forms an excellent
embrocation either alone or mixed with the usual volatile compounds and extracts.
But the oil may be applied alone with advantage. And likewise for sanitary or
antiseptic purposes.

page_text: To reduce the compounds electrolytically, I take the product and melt it in a
stoneware or lined-iron tank or other inert vessel, or in solution in alcohol, acetic
acid, or other solvent, rendered alkaline by the addition of alkali, and employ
electrodes of platinum or carbon. At the same time a current of steam and air may
he employed and any of the oxidising agents added as before mentioned. The anode
may be of an amalgam of alkali metal, as mercury-sodium, lead-sodium, or the like,
in which case, of course, the soluble metal combines with the anion. Other soluble
metals as zinc or aluminium or magnesium may be employed for the same purpose.
Oxygen to the compound is supplied where sodium hydroxide is in solution with it
or other oxy-salt.
To obtain the artificial camphor crystals free from adherences I wash them with
a solution of itself or similar body, as natural camphor, already saturated, as alcoholic
or other solution, previously slightly heated, then filter press or dry in centrifugal
seive, and melt the crystals into moulds, under pressure, so that a clear compact
mass is obtained of maximum boiling point, suitable, alone or melted with natural
.gum camphor in varying proportions, for such purposes as celluloid and other
manufactures, and for the basis of some carbon-compound dying materials.
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. The reduction and oxidation of turpentine hydrochlorides to oxy-camphor by
alkalis and alkaline earths and hot air substantially as set forth.
2. The treatment of turpentine, turpenes, camphene or its isomers, or the like
compounds, by peroxides of the alkalis or alkaline earths substantially as described.
3. The manufacture of isomers of camphor, as oils and solids, by treating terpenes,
turpentine, turpentine hydrochloride or its equivalent, with peroxides substantially
as set forth.
4. The dechloridisation of artificial camphor' by alkalis, or alkaline earth, at
elevated temperatures, in the process of distillation and purification substantially
as set forth.
saturated
5. The cleansing of the manufactured crystals by treatment with a
solution at normal or slightly elevated temperatures substantially as set forth.
6. In the manufacture of artificial camphor' from turpentine, the utilisation of the
uncrystallizable oils produced as a by-product in such manufacture for the purposes
of a solvent for gums and such like, for medicinal, antiseptic or sanitary purposes,
and as an adjunct in oxidising oils and vulcanising oils and rubbers substantially as
set forth.
7. The treatment of halogen combinations of the turpenes by reducing and
oxidising agents substantially as and for the purpose set forth.
8. The electrolytic reduction and oxidation of terpene-halogen compounds
substantially as set forth.
9. The oxidation of the base resulting from the reduction of turpentine hydro-
chlorides by alkalis, by heated air, peroxides, or other oxidising agent, substantially
as set forth.
Dated this 17th day of December 1896.
JAMES C. RICHARDSON.