IMPROVEMENTS IN THE MANUFACTURE OF CANDLES AND OILS, AND IN THE TREATING OF FATTY AND OILY MATTERS, AND IN THE APPLICATION OF CERTAIN PRODUCTS OF FATTY AND OILY MATTERS
Year: 1850

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CHARLES
HUMFREY, of Downing College, Cambridge, M.A., send greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Royal Letters Patent under the Great Seal of the United Kingdom of Great
Britain and Ireland, bearing date at Westminster, the Twenty-third day
of April, One thousand eight hundred and fifty, in the thirteenth year of
Her reign, did, for Herself, heirs and successors, give and grant unto me,
the said Charles Humfrey, my exors, admors, and assigns, Her especial license,
full power, sole privilege and authority, that I, the said Charles Humfrey, my
exors, adiñors, and assigns, or such others as I, the said Charles Humfrey, my
exors, adiñors, or assigns should at any time agree with, and no others,
from time to time and at all times during the term of years therein expressed,
should and lawfully might make, use, exercise, and vend, within England,
Wales, and the Town of Berwick-upon-Tweed, and in the Islands of
Guernsey, Jersey, Alderney, Sark, and Man, and also in all Her said
Majesty's Colonies and Plantations abroad, my Invention of "IMPROVEMENTS
IN THE MANUFACTURE OF CANDLES AND OILS, AND IN THE TREATING OF FATTY
AND OILY MATTERS, AND IN THE APPLICATION OF CERTAIN PRODUCTS OF FATTY
AND OILY MATTERS;" in which said Letters Patent is contained a proviso
that I, the said Charles Humfrey, should cause a particular description of the

page_text: nature of my said Invention, and in what manner the same is to be per-
formed, by an instrument in writing under my hand and seal, to be inrolled
in Her Majesty's High Court of Chancery within six calendar months next
and immediately after the date of the said in part recited Letters Patent, as
in and by the same, reference being thereunto had, will more fully and at
large appear.
NOW KNOW YE, that in compliance with the said proviso, I, the said
Charles Humfrey, do hereby declare that the nature of my said Invention, and
the manner in which the same is to be performed, are fully described and
ascertained in and by the following statement thereof, reference being had
to the Drawings hereunto annexed, and to the figures and letters marked
thereon, that is to say:-
The Invention consists partly in subjecting almost any kind of oil to certain
processes, whereby its constitution is so changed that it is converted into a
substance resembling sperm oil. That the oil. obtained from the sperm whale
differs essentially from all other oils is well known, but I am not aware that
any one has hitherto explained the cause of this remarkable difference.
Although the processes herein-after described certainly convert all the oils I
have tried into an oil having the peculiar qualities of sperm oil, I am not
prepared to assert that the theory of such conversion which I am about to
explain is correct, but I believe it to be so. All or nearly all the oils known
in commerce have the same chemical constitution (excepting sperm oil), and
comprising them all under the term "oline," consist of oleic acid combined
with glycerine (the protoxide of glycerule); they are also bibasic, and each
atom of oleic acid being combined with two atoms of glycerine, oline,
chemically speaking, is the "basic olate" of the protoxide of glycerule. If
oline be exposed to the air or to oxygen gas, or still more rapidly to nitrous
or hyponitrous gas, a change in its constitution is effected, oxygen gas is
absorbed, one or other of the elements of the oline is peroxidized, and a great
quantity of a peculiar gummy substance is produced. Sperm oil is not sus-
ceptible of any such change, hence its value for lubricating machinery. It is
generally supposed that the oleic acid is the element thus peroxidized, and that
a new fatty acid in a state of higher oxidation, called elaidic, is formed, which
remaining with the glycerine, forms a new fatty body called "elaidine;" but
this theory is not supported by any very decisive experiments, and it entirely
fails to account for the invariable production of the gummy matter, the
"corps rouge" of the French chemists. But if we consider that the glycerine
is peroxidized, and that the two atoms of protoxide of glycerule becomes two
atoms of deuxtoxide of glycerule, much of the difficulty disappears. It is a

page_text: well known chemical law, that in all the oxysalts the oxygen in the acid bears
an invariable ratio to the oxygen in the base, and that if any base in combi-
nation with an acid, and forming therewith a neutral salt, be susceptible of two
states of oxidation, and pass from the protoxide to the deuxtoxide state, half
the quantity will suffice fully to saturate the combined acid, and the other half
will be set free. Hence it follows that if the glycerine of the neutral oline be
peroxidized, half the quantity or one atom only will remain combined with
the oleic acid forming the neutral olate of the deutoxide of glycerule
(elaidine), and the other atom must be be thrown out of combination and set
free; and it is this elimminated atom of glycerine or possible deutoxide of
glycerule which I believe to be the gummy matter or "corps rouge" which
always results from the transformation. If this view of the subject be correct.
oline, by absorbing oxygen, is converted into the olate of the deutoxide of
glycerule mixed with one atom of elimminated glycerine, or may be deutoxide
of glycerule; and if by any means we can remove this latter we shall obtain
pure perolate of glycerine, and I believe the oil of the sperm whale to be
simply this perolate of glycerine. In warm-blooded carniverous animals the
oxidation of the oline forming part of their food takes place during the pro-
cesses of respiration and digestion, and the fat of such animals consists of eleic
and stearic acids combined with deutoxide of glycerule (elaidine and mar-
garine), and it is not improbable that the elimminated glycerine may perform
some important function in the animal economy. Now the habits and
organization of the sperm whale are precisely such as would effect this change
in the most complete manner; it lives exclusively on animal food, and is pro-
vided with air-breathing lungs, well adapted to oxidize the oline he feeds on
and convert it into perolate of glycerine. From experiments, which it would
here be out of place to detail. I cannot doubt that the chemical form of sperm
oil is the olate of the deutoxide of glycerule, whatever may be the theory of
its production; and if by any artificial means we can obtain pure perolate of
glycerine it will possess the essential properties of sperm oil, and the processes
herein-after described, as applied to oline, appear perfectly to accomplish this
object. If "stearine," comprising under that term the concrete portion of
fatty bodies, be subjected to the same oxidation, the same phenomena result;
its basic glycerine is peroxidized, part of it (probably half, exactly as stearic
like oleic acil bibasic) is eliminated in the form of a yellowish gummy
substance, and the other half, converted into deutoxide of glycerule, remains
combined with the stearic acid present, and fully saturates it, forming there.
with the neutral stearate of the deutoxide of glycerule (margarine). The
conversion of oline into perolate of glycerine is attended with somewhat

page_text: anomalous results. Some olines are rendered much more concrete, while
others are scarcely affected in that respect. The solidifying action is in some
cases very remarkable, as with olive oil, the oline of tallow, and some others.
If common tallow, for instance, which may be considered as a mixed olate,
and stearate of glycerine be treated as herein-after described, a material will
be obtained of great hardness, nearly free from smell, and possessing much
greater inflammability than the tallow used, and may be moulded into a plaited
wick candle without any further preparation. The persterate and perolate
of glycerine, besides being more inflammable, differ from the fatty body from
which they are made in being quite unchangeable by exposure to the air. If
perfectly fresh tallow, which may be obtained free from smell or nearly so; or
freshly expressed oil of any kind, be exposed some short time to the air, they
become gradually more and more rancid; the glycerine is, in fact, slowly peroxi-
dized, and the elimminated portion (the gum) becoming rancid, is the cause of
their smell; but if the basic glycerine of either stearine or oline be once pushed
to its ultimate state of oxidation, and the elimminated glycerine be removed,
no such change can possibly take place, and the resulting fatty body will
become neither rancid nor gummy, however long exposed to the air; and it is
this unalterability that gives sperm oil, for the purpose of lubricating machi-
nery, its great commercial value. To obtain, then, these two products, the
perstearate and perolate of glycerine, in a state fit for practical purposes, two
things are required,-
Firstly, to convert the basic glycerine of the fatty body into deutoxide of
glycerule; and,
Secondly, to remove the elimminated gummy matter.
The first operation without the second is, for the above purposes, perfectly
valueless.
For the sake of brevity I will describe the processes as applied to "oline;"
and as the same treatment is applicable to "stearine" it will not be requisite
to repeat the description.
Having selected any oline, say the liquid portion of palm or cocoa-nut oil,
which are both moderate in price and of constant production, the solid portions
being valuable for candle making, the first operation is to subject it to the
oxidizing action of nitrous or hyponitrous gas; and to effect this economically
I avail myself of a very remarkable property possessed by these gasses. If
through a vessel containing oline we pass a current of these gasses, or either
of them, they part the nitrous gas, with two, and the hyponitrous gas with one,
atom of their combined oxygen, and are both reduced to the state of deutoxide
of nitrogen, and the deep orange-colored vapours are rendered perfectly colour-

page_text: less. Now, deutoxide of nitrogen possesses the property of taking from
atmospheric air, or from any gas containing free oxygen, sufficient oxygen to
reconvert itself into a mixture of nitrous and hyponitrous gasses. If water be
present, which must be avoided, some little nitric acid will be formed at the
expence of the nitrous gas. Hence it is obvious that if we deoxidize these
gasses by passing them through oline and reoxidize them by admixture with
atmospheric air; and again pass them through oline, and so on alternately, a
very large quantity of oline can be oxidized rapidly and cheaply, the gasses
transferring the oxygen derived from the air to the oline subjected to their
action. If the operation be performed in an ordinary Woolf's apparatus, so
arranged that the first, third, fifth, &c. jars contain oline, and the second,
fourth, sixth, &c. jars are provided with the means of forcing in atmospheric
air, the process can be' very conveniently observed. The orange nitrous fumes
passing through the oline in No. 1 part with oxygen and become transparent
and colourless; passing thence into No. 2 they re-acquire at the expence of
the admitted air their lost oxygen and their colour. In No. 3 they are again
deoxidized by the oline and rendered colourless; and in No. 4 again recover
their oxygen and their colour, and so on until the residual azote of the admitted
air becomes so bulky as to impede the process.
Attached to. this Specification I have added a Drawing and description of
an apparatus which I think convenient for performing the operation, but I do
not confine myself to the details; and it is only by working on an extensive
scale that the most eligible form of apparatus can be determined. The use of
nitrous fumes in the manufacture of the sulphuric acid seems identical with
this action, as any one familiar with that process cannot fail to observe. The
variable qualities of oline and the uncertainty which exists as to the atomic
weight of glycerine, renders it in possible to give any definite practical rule to
détermine the proper point at which to stop the process. Theoretically, it should
be stopped when the whole of the protoxide of glycerule is exactly converted into
deutoxide of glycerule, and it is very important to attain that object. In those
cases where a considerable change in solidity results, and in all there is some,
this point is not difficult to fix, as the point of maximum hardness will be found
very accurately to correspond with the complete peroxidation of the glycerine.
If the. oline be cold, say below 96° Fabrenbeit or thereabouts, some nitrous.
gas will 'condense, which it is better to prevent; but care must be taken to
regulate the temperature, as heat is very rapidly developed, and even in a
small jar, and notwithstanding the cooling effect of the large quantity of air
blown in, the temperature will advance from 90° or thereabouts to 130° and
upwards as the oxidation progresses. It is not improbable that animal heat

page_text: is to some considerable extent caused by the oxidation of the glycerine of fatty
bodies by the action of the lungs. The oline, after this first operation, will
have become darker in color, have a good deal of smell, and be mixed with a
very large quantity of a yellowish brown gummy matter, some of which will
be found adhering to the sides and bottom of the vessel containing it. It
presents, in fact, the appearances, greatly exaggerated, of oline which has
been a long time exposed to the air. All these appearances are caused by the
elimminated glycerine, which it is secondly requisite to remove. Now, glycerine,
as also this elimminated yellow gummy matter, is soluble in alcohol, in ether, in
some spirits, such as pyroligneous in acids, though slightly, and even to some
small extent in water, and in alkaline solutions to almost any extent. Passing
by the use of alcohol, ether, and spirit as impracticable both on account of their
cost and from the solubility of oline in them, and of acids as apt to injure the
product, and of water as quite inadequate for the purpose, there remains only
alkaline solutions to accomplish the object in view. But alkalis, especially
caustic alkalis, which are the most perfect solvents of glycerine, act with
great energy on oline, converting it into soap, and unless the saponification
could be prevented, it would be impossible to use alkaline solutions to wash
out the glycerine. Many ways might be suggested for accomplishing more
or less perfectly this object, but the following process I think is the most
convenient, and will, if carefully performed, completely wash out the gummy
matter and saponify little, if any, of the oline:-To a solution saturated, or
nearly so, of chloride of sodium (common salt) in water, add about two or
three per cent. of alkimetral caustic soda; the oxidized oline, cold enough to
be just liquid, must be well mixed with its own bulk at least of this alkaline
solution, also cold. The glycerine dissolved by or probably combining with
the alkali, will cause the whole to set into a stiff mass, which should be left
for some hours, or even a day or two, undisturbed. After a time, and it is
better to give plenty of time, the mixture must be first gently heated to about
150° to 160° Fahrenheit; and when part of the alkaline liquid holding the
glycerine in solution has settled to the bottom, the heat may safely be pushed
to the boiling point. The solution of glycerine in the alkali will be a deep
orange color, and on cooling will set into a firm jelly, and the perolate of
glycerine, which, if properly treated, will be bright and clear, and free from
the least trace of the glycerine or gum, will float on the top of it, and can be
drawn or poured off without the slightest difficulty. It is important to provide
an abundant solvent for the elimminated glycerine, and I think it generally
expedient to use even more of the alkaline solution than above directed, even
if the per-centage of alkali be reduced. As the product will be more or less

page_text: concrete, it must be separated into liquid oil and solid fat by the ordinary
processes of crystallization, bagging, and pressing. I am aware that fatty
bodies have heretofore been subjected to the action of nitrous and hypo-
nitrous gasses, and that alkalies and salt solutions have been used for
refining fats and oils. What therefore I claim under this part of my Inven-
tion is,―
Firstly, the oxidizing. oline and stearine by the agency of nitrous and
hyponitrous gasses, alternately deoxidized by passing them through the fatty
body, and reoxidized by admixture with atmospheric air, preferring the mode
and apparatus herein described.
Secondly, the removing the elimminated glycerine or peroxide of glycerule
or gummy matter from oline and stearine that have been artificially oxodized
by the use of alkaline solutions, preferring the process described; and,
Thirdly, the combination of the two processes for the purpose of obtain-
ing pure perolate and perstearate of glycerine. If in the place of
acting on oline and stearine, I oxidize by the same process oleic and
stearic acid, a change in their constitution, chemically identical, is effected;
but I am not aware that any purpose of practical utility is answered by
thus acting on stearic acid, though such may hereafter be the case, and
as the process is the same for both I shall confine myself to oleic acid.
Oleic acid, though commonly called an acid, and having in fact some acid
properties, is as absolutely a neutral salt as oline, the two atoms of glycerine
(protoxide of glycerule) in the latter being exactly replaced by two atoms
of water (protoxide of hydrogen) in the former, and oleic acid is, more
correctly speaking, the "basic olate of the protoxide of hydrogen." Now, if by
the action of the oxidizing gases the basic water be converted into deutoxide
of hydrogen, half the quantity, that is, one atom thus peroxidized will
remained combined and fully saturate the oleic acid present, forming the olate
of the deutoxide of hydrogen (elaidic acid), and in lieu of an elimminated
atom of glycerine we ought to obtain an elimminated atom of water, which
is precisely what does take place. If stearic acid be thus treated, we obtain
an atom of elimminated water and the stearate of the peroxide of hydrogen
(margaric acid). In all oleic acids I have tried (and I believe generally) this
change in constitution is attended with a great change in solidity, and the
process may usefully be employed to transform the liquid oleic acids of
commerce, and cheap, because liquid, into a concrete substance, this resulting
fatty acid is highly inflammable, and is also useful for purposes described in
the concluding part of this Specification. The only precaution requisite is,
to stop the process at the exact point when the oleic acid is just converted

page_text: into the olate of the deutoxide of hydrogen. Assuming, and I believe correctly,
that the combining number of oleic acid is 358, then every three hundred and
fifty-eight parts of acid acted upon will require just eight parts of oxygen to
effect the conversion; and if the elimminated water be prevented from
evaporating, or be condensed and weighed, this exact increase in weight
will correspond with the maximum point of hardness, and with the complete
peroxidation of the basic water. But practically it is more convenient to
note the change in specific gravity. Taking the specific gravity of distilled
oleic acid obtained from palm oil as an example, its specific gravity at 100
Fahrenheit is 887, and that of the resulting olate of deutoxide of hydrogen
at the same temperature is 904. This rule is of casy application, and suffi-
ciently exact for all practical purposes. I am aware that nitrous and hypo-
nitrous gasses have been used to solidify oleic acid, and I therefore claim only
the acting on fatty acids by these gasses alternately deoxidized by passing
them through the acid and reoxidized by admixture with atmospheric air, and
I preper the mode and apparatus described for effecting this operation.
DESCRIPTION OF THE DRAWING.
.a, a, a, is a long shallow vessel shewn in vertical section, to contain the
oline, and may be made of lead, pottery, cement, or other convenient material,
as. it is expedient to expose as much surface as may be to the action of the
nitrous fumes. This vessel may be made six inches deep, four feet wide, and
twenty-four feet long. b, b, b, is a cover to fit this air-tight, and from it
descend small partitions c, c, c, dipping just below the surface of the oline;
d, the outlet, leads into a shaft e, e, through which is driven a jet of high-
pressure steam; f,f, is a vessel or chamber of any convenient form, in which
the nitrous fumes are generated; 9, 9, 9, are tubes furnished with stopcocks
or valves, and their ends dip just below the surface of the oline. An arrange-
ment must be made to keep the oline at the proper temperature (between 96
and 120) Fahrenheit, which can easily be done by laying a coil or two of
steam pipe in the vessel a, a, a, and to insure a uniform action the charge of
oline must be made to circulate, which can be done by a pump taking it from
hand returning it at i. The action of the steam jet will cause a partial
vacuum in the whole, apparatus, and the nitrous fumes will be drawn in the
direction of the arrows, passing over the surface of the oline, and through it
at c, c, c; by opening the cocks in 9, 9, 9, any required quantity of air can be
allowed to flow in and can be regulated at pleasure. It is obvious that the
vacuum formed by the steam jet can be obtained by a fanner or pump, or
other contrivance, but I think a steam jet very convenient; also that instead

page_text: of drawing the nitrous fumes and the air through the apparatus they could be
forced through, but I much prefer the mode described, as the nitrous fumes
under pressure are apt to condense, and by working by exhaustion the joints
of the cover will not require to be made particularly air-tight, and generally
the machine is more simple and cheaper.
The Invention further relates to combining fatty acids with the oxides and'
peroxides of metals, with many of which they form very beautiful colors.
The pigment known as "verdigris" is an acetate of copper; if in the place
of acetic acid oleic acid be used, the olate of copper, a pigment very closely
resembling verdigris, is obtained. The combination of oleic acid with pro-
toxide of copper can be effected in many ways, but I prefer the following:
The oleic acid is first to be combined with an alkali, by preference with soda,'
so as to form a perfectly neutral olate of soda, then take any protosalt of
copper, say the sulphate, and dissolve it in boiling water, add to it by degrees:
the olate of soda, taking care to leave always a slight excess of the copper
salt; double decomposition immediately takes place, and I obtain the olate of
protoxide of copper and sulphate of soda. The cake of color on cooling can'
be removed, and after well washing, to remove adhering sulphate of soda and
sulphate of copper, is fit for use. Stearic acid may be used instead of oleic,
but without any particular advantage. The only precautions requisite are to
make both the olate of soda and the sulphate of copper perfectly neutral
before mixing them. Other metallic protoxides can be combined with fatty
acids in the same way. The pigments known as "Scheel's green
"and
"emerald green" are some (rather uncertain) combinations of copper with
arsenious and acetic acids. If instead of acetic acid oleic acid be used, a
corresponding colored compound will be obtained. This can be effected by
boiling the olate of soda with arsenious acid in excess, decanting the clear
supernatant liquor, and decomposing by a neutral protosalt of copper, and I
think this is the best way of proceeding, but the arsenious acid may be
introduced at almost any stage of the process. The resulting color is always
the same.
A second series of coloured salts are obtained by combining oleic
acid with the peroxides of metals. For this purpose, instead of using oleic
acid (the olate of protoxide of hydrogen) I must use elaidic acid (the olate
of the peroxide of hydrogen), the preparation of which has been before
described. If this fatty acid be combined with soda I obtain a deep reddish-
brown solution, which I believe to be the olate of the peroxide of sodium.
Taking care to make this soap perfectly neutral, and decomposing it with
neutral sulphate of copper, I obtain sulphate of soda and the olate of the
peroxide of copper. If a soap be made with soda and perolate of glycerine,

page_text: (elaidine) and decomposed as above, a somewhat similar color will result,
but it is better to use the fatty acid. Other metals may be substituted for
copper, and stearic acid used in the place of oleic, but as before stated, I do
not think any advantage will be obtained by the substitution of stearic for
oleic acid. A third series of colors are obtained as follows:-If instead of
stopping the oxidation of oleic acid, as before directed, when its specific
gravity has advanced to .904, corresponding or nearly so to the exact peroxi-
dation of the basic water, the process be continued until the specific gravity
has advanced to .970, a very complicated change seems to have taken place
in the fatty acid, which it would be here out of place to explain. The fatty
acid on
having attained this specific gravity (I do not confine myself to the
exact point) will be nearly as liquid as it was at first, and by combining it
with soda a neutral soap will be obtained, the solution of which has a much
greater intensity of color than the perolate of soda before described; it is, in
fact, almost black; and decomposing this solution with a neutral salt of
copper, iron, zinc, manganese, tin, or some other metals, I obtain colored salts
of great brilliancy from the copper, a leaf green from the iron, a mahogany
brown from the zinc, from the manganese yellow, from the tin bright
yellow, &c.
I claim under this last part of my Invention, the combining fatty acids with
certain metallic oxides and peroxides, for the purpose of obtaining colored
salts to be used as pigments and dyes.
In witness whereof, I, the said Charles Humfrey, have hereunto set my
hand and seal, this Twenty-third day of October, in the year of our
Lord One thousand eight hundred and fifty.