IMPROVEMENTS IN THE MANUFACTURE OF MINERAL OILS
Year: 1855

page_text: LETTERS PATENT to Hiram Hyde, of Truro, Nova Scotia, Gentleman, for.
the Invention of "IMPROVEMENTS IN THE MANUFACTURE OF MINERAL OILS"
A communication.
Sealed the 22nd January 1856, and dated the 24th November 1855.
PROVISIONAL SPECIFICATION left by the said Hiram Hyde at the
Offico of the Commissioners of Patents, with his Petition, on the 24th
November 1855.
I, HIRAM HYDE, of Truro, Nova Scotia, Gentleman, do hereby declare the
nature of the said Invention for IMPROVEMENTS IN THE MANUFACTURE OF
MINERAL OILS, to be as follows:-
This Invention relates to a mode or modes of obtaining a new preparation
of oil from mineral hydrocarbons, or the well-known distillates of such sub-
stances. As an example of the materials which will yield beneficially the
new preparation of oil I may mention the following, which have been used with
success, viz., Seneca oil, rock oil, Barbadoes and Rangoon tar, and other fluid
petroleums; also the bitumen known as chapapote, Trinidad pitch, asphaltum,
and also cannel, boghead, and other analogous coals and shales impregnated
with bitumen.
In treating the oils the following process is adopted, and, with slight
variations, it applies also to obtaining oil from the other substances:
This improved process may be considered as distinct from fractional
distillation, and the substance obtained differs also in physical and chemical
qualities. By a rapid distillation, at a temperature of 600° to 850 suddenly

page_text: applied, the petroleum is decomposed into two distillates; a portion passes off
below 600°, which is rejected, but that collected at 600° to 850 F., as a brown
bituminous oil, is retained as a basis for the new manufacture.
The rock oil to be used is introduced into an iron still, fitted with a
condenser. Fire being applied, a rapid combustion is obtained until the fluid;
marks 590° to 600° F.; the condensed products are removed from the
recipient, and the fire steadily increased to carry over rapidly all the vapor
which will rise below 850° F. If the heat be continued until nothing but
coke remains, the last or charred product may be used in the next following
distillation of natural petroleum.
The distillate obtained between 600° and 850° F. is crude, and would if
re-distilled give colored bodies, unlike thoso to be obtained; it is therefore
subjected to the action of sulphuric acid, and subsequently to a solution of
caustic soda. After the withdrawal of the soda solution, a solution of manganate
or permanganate of potash or soda must be added and mixed with the oil.
When the manganate has subsided, and full oxidation of pyretine and
analogous compounds have been thus effected, the oil is placed in a clean iron
still with a solution of caustic soda. On the application of heat tho soda
solution loses its water, and as the temperature rises the vapors of volatile
bodies are condensed, until the heat of the fluid oil is 580° to 600° F., when
the recipient for purified oil is adapted, and the heat rapidly increased, until
the condensing products assume a dark hue; the temperature will then be
about 850° F. If heated steam be used above the materials of the charge,
nearly the whole will be vaporized without the production of brown color.
When the soda solution has been removed, the oil must must be washed by
jets of steam to remove soapy compounds, and then exposed in shallow pans to
direct sunlight, until it becomes bright and clear. Some petroleums yield a
pure product without requiring the last distillation here named. The whole
number of operations will convert any of the petroleums into an improved oil.
In manufacturing the improved oil from the bitumens and the coal series
above indicated, the process above explained is also pursued, with slight modi-
fications, dependent on the nature of the materials under operation. When
operating with the coal series, it is preferred to take the crude distillate of
those substances (which may be readily obtained in the market), and after
washing out by means of caustic soda the acid hydrocarbons, the tarry fluid is
subjected to the distillatory and purifying processes above described, and an
oil whose boiling point is above 600 Fahr. is obtained.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Hiram Hyde in the Great Seal Patent Office on the
24th May 1856.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, HIRAM
IIYDE, of Truro, Nova Scotia, Gentleman, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fourth day of November, in the year of our
Lord One thousand eight hundred and fifty-five, in the nineteenth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Hiram Hyde, Her special license that I, the said Hiram Hyde, my execu-
tors, administrators, and assigns, or such others as I, the said Hiram Hyde,
my executors, administrators, and assigns, should at any time agree with,
and no others, from time to time and at all times thereafter during the
term therein expressed, should and lawfully might make, use, exercise, and
vend, within the United Kingdom of Great Britain and Ireland, the Channel
Islands, and Isle of Man, an Invention for IMPROVEMENTS IN
THE MANU-
FACTURE OF MINERAL OILS, being a communication from abroad, upon tho
condition (amongst others) that I, the said. Hiram Hyde, by an instrument
in writing under my hand and seal, should particularly describe and ascer-
tain the nature of the said Invention, and in what manner the same was to
bo performed, and cause the same to bo filed in the Great Seal Patent Office
within six calendar months next and immediately after the date of the said
Letters Patent.
NOW KNOW YE, that I, the said Hiram Пyde, do hereby declare the
nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say):-
This Invention relates to a mode or modes of obtaining a new preparation
of oil from mineral hydrocarbons, or the well-known distillates of such
substances. In order that the nature of this Invention may be clearly under-
stood, I will first explain the mode of operating upon the oils obtained by
decomposing fluid and semi-fluid petroleums; I will next explain the mode of
operating to obtain a new preparation of oil from solid bitumens; and, lastly,
the mode of treating the crude distillatory products of cannel, boghead, and
other analogous coals, for the purpose of obtaining a new preparation of oil
therefrom.
The first part of this Invention consists in the application of improved
chemical methods in the separation and subsequent purification of oil, obtained

page_text: by decomposing fluid and semi-fluid petroleums, so as to obtain a definite and
useful oil from any member of this class. For this purpose I take Seneca oil,
rock oil from coal or salt mines, Barbadoes and Rangoon tar, or any fluid
petroleum of the naphtha class of natural hydrocarbons, and so decompose the
part which distils at a high temperature, as to form an oleaginous body, which
does not exist ready formed in it. The researches of the Inventor have
proved that these bodies, which have been supposed to consist of mixtures of
volatile oils and naphtha, with a pitch-like residue, can be changed by heat
quickly applied (somewhat as coal is changed into gas tar and water by
sudden heat) into volatile and less volatile rough products, with the occurence
of very little matter of an intermediate kind. But more especially when the
denser rough product is brought in contact with alkalies at a high and low
temperature, with the intervention of acid to remove alkaline or basic bodies,
the proximate constituents of this rough product will be caused to break up
and re-arrange themselves anew to form a substance unlike any heretofore
obtained, and which, as an adjunct to other oils, or alone, has valuable properties.
Thus, by what is called fractional distillation, the petroleums may be resolved
into different fluids boiling at two hundred and twelve degrees Fahrenheit,
three hundred degrees Fahrenheit, three hundred and fifty degrees Fahrenheit,
four hundred degrees Fahrenheit, and some at four hundred and fifty degrees
Fahrenheit, when more than one half will have passed off, leaving 1 pitch in
the retort. These different educts when purified and adjusted to fixed boiling
points have received different names, those with the higher boiling points being
called "paraffine" oil. Now this improved process may be considered as
distinct from fractional distillation, and the substance obtained differs also in
physical and chemical qualities. By a rapid distillation, at a temperature of
six hundred degrees to eight bundred and fifty degrees suddenly applied, the
petroleum is decomposed into two distillates. That portion which passes off
below six hundred degrees is rejected as unsuited to the present purpose, but
that collected at six hundred degrees to eight hundred and fifty degrees
Fahrenheit, as a brown bituminous oil, is retained. This brown body is the
product to which the process now to be described is applied, and constitutes in
fact the basis of the new manufacture.
The rock oil or fluid bitumen to be used is first deprived of any water that
may adhere thereto, and it is then introduced into an iron still fitted with a
condenser. The still body must be deep in a large furnace, with draft sufficient
for active combustion. Fire being applied, a rapid combustion is obtained,
until a thermometer immersed in the fluid marks five hundred and ninety
degrees to six hundred degrees Fahrenheit. The condensed products are

page_text: removed from the recipient, and the fire steadily increased to carry over
rapidly all the vapor which will rise below eight hundred and fifty degrees
Fahrenheit. The measurement of this temperature is best effected by
an iron bar, having cavities for the bulb of the thermometer at different
distances from the end, immersed in the hot contents of the still, graduated by
previous trials. It is also an useful indication to withdraw from time to time a
few drops of the condensing oil, and when this becomes evidently charred, to
cease to collect for use the residue. If the heat be continued till nothing but
coke remains, the last or charred product may be used in the next following
distillation of natural petroleum.
The distillate obtained between six hundred degrees and eight hundred and
fifty degrees Fahrenheit is crude, and would if re-distilled give colored bodies,
unlike those to be obtained. One hundred gallons of the deep brown distillate
are to be placed in an agitator of lead, and subjected to a violent churning
motion, with one hundred pounds of oil of vitriol (sulphuric acid, sixty-six
degrees Beaumé), the temperaturo being as high as ninety degrees Fahrenheit,
for two hours. Basic hydrocarbons combine with the strong acid, while some
products are charred, and subside with the acid after about six hours. When
the impurities have subsided, the oil must be drawn off by cocks at different
levels and placed in another apparatus with five gallons of caustic soda solu-
tion, at thirty-six degrees Beaumé, and agitated three hours, for the purpose of
abstracting acid sulphates formed, as well as any acid hydrocarbons present.
After the withdrawal of the soda solution, a solution of six pounds of manga-
nate or permanganate of potash or soda in two gallons of water must be added,
and mixed with the oil by agitation, continued one hour, at the temperature of
ninety degrees Fahrenheit, and the whole left until by repose the remains
of the manganate have subsided. Full oxidation of pyretine and analogous
compounds having been thus effected, the oil must be placed in a clean iron
still, with four gallons of caustic soda solution, at thirty-six degrees Beaume.
On the application of heat the soda solution loses its water, and as the
temperature rises the vapors of volatile bodies are condensed, until the heat
of the fluid oil is five hundred and eighty degrees to six hundred degrees
Fahrenheit, when the recipient for purified oil is adapted, and the heat rapidly
increased until the condensing products assume a dark hue; the temperature
will then be about eight hundred and fifty degrees Fahrenheit. If heated
steam be used above the materials of the charge, nearly the whole will be
vaporized without the production of brown color. The distillate mixed with
two gallons of caustic soda solution, at thirty-six degrees, for every one hundre:
gallons, and strongly agitated, at one hundred degrees Fahrenheit loses an acid

page_text: body.
After the soda solution has been removed, the oil must be washed by
jets of steam to remove soapy compounds, and then exposed in shallow pans to
direct sunlight until it becomes bright and clear. Some petroleums yield a
pure product without requiring the last distillation here named; the whole
number of operations will convert any of the petroleums into our improved oil.
The general result is a partial destruction of paraffine, and the production of
an oleaginous body, which boils at about eight hundred degrees Fahrenheit,
conferring its properties on the oil obtained.
Under this head of the Invention I claim the production of an oil from the
fluid and semi-fluid petroleums, or bodies of the naphtha class, by the application
of the process above set forth.
The second head of the Invention relates to the production from the various
solid bitumens of oils having highly unctuous qualities and high boiling points,
which permit of their being used alone or with other oils for lubricating
machinery. Combustible oils, and such as entered into the composition of
varnishes, have long been obtained from the solid bitumens; but oils of an
oleaginous consistency, adapted to diminishing friction, have not, so far as I am
aware, been produced from these bodies. The Inventor has found that the
bitumens called chapapote, Trinidad pitch, asphaltum, and elastic bitumen, to
belong to one class of bodies, inasmuch as the result of their proximate
decomposition is so nearly the same that the improved process applies to
them all. They, however, differ from the fluid petroleums and also from tho
cannels chemically. To adapt, therefore, the products from the solid bitumens
to the manufacture of a good lubricating oil, the process requires certain
modifications. Experiment has proved that the solid bitumens differ from the
fluid petroleums in giving more oxidized products; but essentially in this,
that having been solidified by natural changes they do not easily become re-
converted into fluid parts. Thus, they will yield, by the well-known process of
fractional distillation, odorous volatile oils, and leave a residuum, which,
affording by prolonged heat creosote, eupione, and paraffine, leaves a largo
coke as a final product; but by removing at once some of the bodies which
affect the subsequent decompositions, an oil may be produced from the various
solid bitumens, which has a nearly entire unity of composition and physical
and chemical qualities, rendering it valuable in the arts.
To obtain this result, I take the crude bitumen of Cuba, or any of the
naturally solid bitumens, and wash away all dirty matter, and dry, as far as
is possible, the raw material. These bitumens when heated produce much
watery vapour, which, distending the mass, cause it to flow and bubble, so as to
prevent ordinary distillation. Having introduced the bitumen into an iron

page_text: still provided with a suitable condenser, I apply a regulated heat and distil off
all the volatile matter.
The crude product from the bitumen placed in another still is submitted to
a quick fire, until the temperature in the fluid contained in the still is five
hundred degrees Fahrenheit; the receiver being changed, the fire is then
urged, and all that comes over below eight hundred and fifty degrees Fahren-
heit is collected. To this distillate, when placed in a lead agitator, for every
one hundred gallons one hundred and eighty pounds of oil of vitriol (sulphuric
acid, sixty-six degrees Beaumé) is added, and the whole is then strongly agitated,
and the temperature allowed to rise as high as one hundred degrees Fahren-
heit. After the subsidence of the acid, the oil must be removed to another
agitator, and there be treated with six gallons of caustic soda solution, at
thirty-six degrees Beaumé, and by means of a steam coil the soda solution
must be made to boil, water being supplied as it evaporates for one hour.
When the foul soda solution as been withdrawn, and the oil has cooled to one
hundred degrees Fahrenheit, five pounds of manganate or permanganate of
potash or soda in two gallons of water must be added and well agitated with
the oil. The material thus purified must be again distilled from a clean still,
the products boiling from six hundred degrees Fahrenheit to eight hundred
and fifty degrees Fahrenheit being collected, or until they become a brown
fluid as they cool. It will be observed in this distillation that nearly all the
oily matter which rises has a fixed boiling point, about seven hundred and fifty
degrees Fahrenheit, and that very little of the fluids having low boiling points
remain.
The final purification of the distillate is effected by agitating one hundred
gallons with one hundrod pounds of oil of vitriol, as before. After the removal
of the acid, the oil must be treated with one-sixteenth of its volume of caustic
soda solution, at thirty-six degrees Beaumé; by washing away the soda with
water and subjecting the oil to jets of steam for half an hour, all traces of
soap-like compounds can be removed. The oil, after being exposed some days
to the sun's rays, loses a trace of water, and becomes transparent and brilliant,
when it is fit for use.
These steps of the process and proportions of acid and alkaline solution will
purify the crude distillate from any of the known bitumens, but it is not always
necessary that the whole quantity of acid and alkaline solution be used
when creosote, naphthaline, pyretine, and a peculiar smoke oil do not abound,
or where acid hydrocarbons are not largely produced. It will be seen that the
steps of this process bear some resemblance to the operations on fats, when, by
previous treatment of these with sulphuric acid, sulpho-glyceric acid is formed

page_text: and washed away, and the oil in distillation does not then afford acroleine, as it
would do were glycerine present in the oil; but the bituminous crude dis-
tillates contain several bodies which decompose into volatile odorous oils, and
they must be all removed before an uniform oil can be obtained.
Under this head of the Invention I claim the production from the solid.
native bitumens of an oil having a boiling point as high as six hundred
degrees Fahrenheit by the process set forth.
I will now explain the mode of treating crude products obtained by dis-
tilling the coals known as cannel, boghead, Breckenridge, brown coal, peat,
and Albert coals, and shales impregnated with bitumens, so as to eliminate
hydrocarbons from the proximate constituents contained in them. These
hydrocarbons in some cases exist in the crude basis taken for the purposes of
the present Invention; but of these, some are rejected, and others which are
present aro modified by the improved process to which they are submitted, by
which means they are rendered more fixed in their relation to heat, and blended
so as to form a definite compound of an oily character possessed of very valuable
properties. In the following description it will be observed by those who are
skilled in the art that is not intended merely to separate and purify bodies
which have been known before, and as articles of commerce, but by different
steps, applicable only to the particular crude matter of the cannel coal series,
to arrange anew the component parts of crude distillates.
Thus, instead of commencing with the coal, the fluid matter condensed, by
distilling coals of the cannel series, however obtained, is the material employed.
This distillate is subjected in an iron vessel to a careful washing in water to
remove soluble matter.
The washed tar-like fluid, introduced into a agitator, must have all its acid
hydrocarbons removed, by means of successive portions of caustic soda, or
caustic potash, at thirty-six degrees Beaumé added, agitated and withdrawn,
until the solution of alkali appears to become no longer changed even at two
hundred and twelve degrees Fahrenheit. In this step, not only is the removal
of the acids present in a free state effected, but acid salts or combinations of
positive and negative hydrocarbons are decomposed, and their bases eliminated,
while the acid or positive constituent, which is essential to the success of the
other steps of the process, is removed.
The tarry matter removed from the last portion of alkali must be distilled
from an iron retort by naked heat, or heat aided by steam, the distillate being
rejected until the mass in the retort shows the temperature of six hundred
degrees Fahrenheit, when the distillate sought for begins to appear. By
increasing the heat, a large bulk of the distillate is obtained, and when the

page_text: temperature of seven hundred and fifty degrees to eight hundred and fifty
degrees Fahrenheit is reached, the distillate assumes a brown color, at which
point the process is stopped. In the systematic manufacture, it is usual to save
the oil boiling at four hundred and fifty degrees, or below six hundred degrees,
and mix it with that distilling above eight hundred and fifty degrees, adding
them to the next charge in the retort; by the reactions in the retort colored
and basic bodies are formed, requiring for their removal usually two hundred
pounds of oil of vitriol for every one hundred gallons of the distillate, with
agitation for two hours, and repose in air at eighty degrees or ninety degrees,
until subsidence of the acid compound has taken place.
The clear oil must now be washed with five gallons of caustic soda, at thirty
six degrees Beaume, for one hour; this solution withdrawn, six pounds of
manganate of potash or soda dissolved in five gallons of water must be added,
and the whole agitated one or two hours, the temperature being as high as one
hundred degrees Fahrenheit to allow of subsidence of all impurities. The clear
oil must then be transferred to an iron retort and distilled by the gradual
application of heat, with the aid of heated steam above the oil, reserving for
future steps the distillate rising between six hundred degrees and eight
hundred degrees Fahrenheit only. This operation has produced a new quantity
of colored and basic matter, which must be removed by treating one hundred
gallons of the distillate in an agitating apparatus with one hundred pounds of
oil of vitriol, and violently mixing for two hours. After the action of the acid,
the oil must be washed with five gallons of soda solution, at thirty-six degrees
Beaume, by agitation for one hour, and then allowed to subside. The resulting
product being again distilled, with the precautions above stated, will have
become permanent and uniform.
A small amount of acid present must be removed by agitating the distillato
with three gallons of caustic soda solution, leaving the oil for the separation
of the soda solution at a temperature of eighty degrees or ninety degrees
Fahrenheit. After the removal of the oil from the impurities, it must be
thoroughly washed by jets of steam in the usual manner, and subsequently
exposed in shallow pans to the sun's rays, until all moisture has become
dissipated.
The purified oil resulting from these processes is nearly identical with that
obtained from the crude distillate of the petroleums of the naphtha series, and
is applicable to the same purposes. It is not always necessary to subject the
oil to the last distillation here named, as some of the crude distillates are more
easily broken up than others; but it is essential that the oil be freed from all
bodies having low boiling points, and that the solid hydrocarbons, which

page_text: appear in the first steps, be decomposed almost wholly into an oleaginous
body.
Under this head of the Invention I wish it to be understood that I disclaim
the production of paraffine oil, such as has been heretofore made from the
cannel series of coals, at low temperatures, and is well known, and confine
the application of the process to the production of an oil having a high boiling
point, and as nearly free from paraffine as it is possible to produce from such
materials.
What I claim, therefore, under this the third head of this Invention is, the
production from distillates of the cannel coals an oil having a boiling point
about six hundred degrees Fahrenheit by the process above set forth.
In witness whereof, I, the said Hiram Hyde, have hereunto set my
hand and seal, the Second day of May, in the year of our Lord One
thousand eight hundred and fifty-six.
H. HIDE. (.)