IMPROVEMENTS IN THE TREATMENT OF THE REFUSE OR SLUDGE OIL PRODUCED IN THE DISTILLATION OR PURIFICATION OF CRUDE PETROLEUM, ASPHALTE, BITUMEN, AND OTHER SUBSTANCES FROM WHICH HYDROCARBON OILS ARE OBTAINED, THE OBJECT OF SUCH TREATMENT BEING TO OBTAIN USEFUL PRODUCTS THEREFROM."
Year: 1876

page_text: LETTERS PATENT to William Edward Newton, of the Office for Patents, 66,
Chancery Lane, in the County of Middlesex, Civil Engineer, for the Invention
of "IMPROVEMENTS IN THE TREATMENT OF THE REFUSE OR SLUDGE OIL
PRODUCED IN THE DISTILLATION OR PURIFICATION OF CRUDE PETROLEUM,
ASPHALTE, BITUMEN, AND OTHER SUBSTANCES FROM WHICH HYDROCARBON
OILS ARE OBTAINED, THE OBJECT OF SUCH TREATMENT BEING TO OBTAIN
USEFUL PRODUCTS THEREFROM." A communication from abroad by Walter
P. Jenney, of New York City, in the United States of America.
PROVISIONAL SPECIFICATION left by the said William Edward Newton at
the Office of the Commissioners of Patents on the 3rd June 1876.
WILLIAM EDWARD NEWTON, of the Office for Patents, 66, Chancery Lane, in the
County of Middlesex, Civil Engineer. "IMPROVEMENTS IN THE TREATMENT OF THE
REFUSE OR SLUDGE OIL PRODUCED IN THE DISTILLATION OR PURIFICATION Of
CRUDE PETROLEUM, ASPHALTE, BITUMEN, AND OTHER SUBSTANCES FROM WHICH
HYDROCARBON OILS ARE OBTAINED, THE OBJECT OF SUCH TREATMENT BEING TO
OBTAIN USEFUL PRODUCTS THEREFROM."
This Invention has for its object the treatment of the refuse or sludge oil produced
in the distillation or purification of crude petroleum, asphalte, bitumen, and other
substances from which hydro-carbon oils are obtained, the object of such treatment
being to obtain useful products therefrom. Among other useful products a fine
liquid hydro-carbon, also useful resinous substances are obtained and a new and
useful varnish may be produced.
In the purification of hydro-carbon oils produced by the distillation of crude
petroleum, asphalte, or bitumens, or by the destructive distillation of coal resins or
bituminous shales, the oils are agitated with two per cent. or more of concentrated
sulphuric acid in order to remove certain oils contained in the distillate, which
would in course of time absorb oxygen from the air and cause the oil to become
dark colored and gummy, and also to remove tarry substances and the disagreeable
odour. Sulphuric acid combines chemically with these bodies and dissolves them,
forming a dark and heavy liquid which settles on the bottom of the agitator and
can then readily be drawn off from the purified oil; this peculiar compound of
Price Ad71

page_text: sulphuric acid and hydro-carbon oils dissolved in the excess of acid is known as
sludge. If mixed with a little water the compound of acid and oil is decomposed
and produces a weaker acid together with a dark coloured offensive oil which rises
to the surface of the acid and usually is thrown away, no commercial use having
been found for it. This waste product is called "sludge oil."
The sludge as it is received from the oil refiners contains some free illuminating
oil mechanically mixed with it to remove which the sludge is agitated in a tank with
about 5 per cent. of petroleum naptha which dissolves the free oil, and on allowing
the sludge to remain at rest this oil rises to the top and can be removed from the
purified sludge. The sludge is then decomposed by the addition of water, and the
sludge oil which rises to the top of the mixture of acid and water is drawn off and
saved. The sludge oil is then purified by repeated washings with water until the
acid remaining in it is removed. The remaining traces of acid in the oil are then
neutralized by quick lime or caustic soda. The purified oil contains about ten per
cent. of volatile oils, which are obtained by introducing the sludge into a still with
the addition of caustic soda and oxides of lead or manganese to oxidize any sulphur
in the oil. Steam is then blown through the oil, which is kept hot by a fire under
the still or by the use of steam heated to the required temperature. This is con-
tinued until no more volatile oils are removed. The steam is then shut off and the
contents of the still allowed to settle, when a sediment of tarry impurities and soda
subsides from which the pure oil may be drawn off. The oil is then introduced
into a still or tank and oxidized by blowing currents of air through it, the oil being
kept hot either by a slow fire under the still or by a steam coil in the bottoin of the
tank, or by heating the air in a hot blast oven or otherwise to the proper temperature
before it is blown through the oil. The action of the air is continued until the
mixture in cooling is found to be a resinous substance of a greater or less hardness
or consistency. After allowing the contents of the still to settle the hot resin is
drawn off from the sediment of soda and impurities.
The action of the air may be accelerated by adding about two per cent. of the
oxides of lead or mangenese, or about two per cent. of the manganates of soda and
potassa to the oil. These substances act either by giving up oxygen to the oil or
by their presence inducing a combination of the oxygen and the hydro-carbon. An
inferior quality of this resinous substance may be produced by treating the washed
sludge oil in a still with caustic soda and litharge, and blowing a current of hot
air through it. This oxidizes the oil and removes the more volatile portions, which
are distilled off until it is converted into a resinous substance of the required
hardness. To produce the lightest coloured resins the sludge oil is steamed with
five per cent. of soda at a low temperature to remove the more volatile portions,
and is then oxidized and bleached by exposing the oil in shallow tanks covered by
glass to the sunlight, the oil being kept lot and fluid by a steam coil in the bottom
of the tank, and currents of air blown through it to produce the oxidation. Inferior
qualities of sludge oil which contain a large quantity of tarry substances are treated
as follows:-The oil is charged into a still, and caustic soda and black oxide of
manganese are added, and the charge distilled by a current of steam blown through
the oil assisted by a fire under the still; until only tar and coke remain behind. By
the use of steam under pressure, especially when superlicated, the oil can be distilled
with scarcely any decomposition, and the distillate, which is of a yellow or light
red color, can be converted into a superior light coloured resinous substance by
oxidizing it with currents of air at the lowest possible working temperature. A
good varnish may also be produced from the resinous substance before described
by dissolving or mixing it either with or without the aid of heat with such
solvents as will completely and perfectly dissolve the resinous substance and
produce a useful varnish. Petroleum naphtha readily dissolves the resinous substance
(even without the aid of heat) and produces an excellent varnish which dries very
quickly. Turpentine completely dissolves the resinous substance, especially when
aided by heat, and produces a good varnish. Benzol and coal tar naphtha also
quickly dissolve the resinous substance and produce a varnish. Linseed oil and

page_text: other drying oils, or a mixture of these with turpentine, petroleum, or naphtha
dissolve the resinous substance readily when aided by heat, forming slow drying
oil varnishes. A mixture of drying oil and turpentine or drying oil and petroleum
naphtha quickly dissolve the resinous substance, forming a more or less quickly
drying oil varnish as the proportions of the ingredients are varied. An excellent
varnish drying very quickly consists of resinous substance, one pound, petroleum
naptha, one gallon. Dissolve cold. For a good oil varnish take resinous substance
ono pound and 8oz., petroleum naphtha, one gallon, linseed oil, one pint. Dissolve
by the aid of a moderate heat. For the petroleum naphtha oil of turpentine may
be substituted. For waterproofing paper the following is best, resinous substance,
12 oz., oil turpentine, 1 gallon. Dissolve by aid of a moderate heat.
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by the
said William Edward Newton in the Great Scal Patent Office on the 27th
October 1876.
WILLIAM EDWARD NEWTON, of the Office for Patents, 66, Chancery Lane, in the
County of Middlesex, Civil Engineer. "IMPROVEMENTS IN THE TREATMENT OF
THE REFUSE OR SLUDGE OIL PRODUCED IN THE DISTILLATION OR PURIFICATION
OF CRUDE, PETROLEUM, ASPHALTE, BITUMEN, AND OTHER SUBSTANCES FROM WHICH
HYDROCARBON OILS ARE OBTAINED, THE OBJECT OF SUCH TREATMENT BEING TO
OBTAIN USEFUL PRODUCTS THEREFROM." Being a communication to me from abroad
by Walter P. Jenney, of New York City, in the United States of America.
In the purification of hydro-carbon oils produced by the distillation of crude
petroleum, asphaltes, or bitumens, or by the destructive distillation of coal, resins,
or bituminous shales, the oils are agitated with two per cent. or more of con-
centrated sulphuric acid, 66° B 1.86 sp. gr., in order to remove certain oils contained
in the distillate, which would in course of time absorb oxygen from the air and
cause the oil to become dark colored and gummy, and in order also to remove
tarry substances and the disagreeable odour. Sulphuric acid combines chemically
with these bodies and dissolves them, forming a dark and heavy liquid which
settles on the bottom of the agitator and can then readily be drawn off from the
purified oil.
This peculiar compound of sulphuric acid and hydro-carbon oil
dissolved in the excess of acid is known as sludge. At present it is purchased by
superphosphate manufacturers, who mix it with a little water which decomposes the
compound of acid and oil, thereby producing a weaker acid (about 50° B) which is
used in the manufacture of super-phosphate of lime, and also a dark colored
offensive oil which rises to the surface of the acid and usually is thrown away, no
commercial use having been found for it. This waste product is called "sludge
oil," and the object of the present Invention is to deal with this "sludge oil" and
obtain useful products therefrom.
The mode of practising the present Invention will be understood by the following
explanation of the process.
The sludge as it is received from the oil refiners contains some free illuminating
oil, which is mechanically mixed with it, and in order to remove which the sludge is
agitated in a tank with about five per cent. of petroleum napthla (sp. gr. 70° B), the
naphtha dissolves the free oil, and on allowing the sludge to remain at rest froni
twelve to twenty-four hours the naphtha rises to the top and is removed from the
purified sludge. The sludge is then decomposed by the addition of water, and
the sludge oil which rises to the top of the mixture of acid and water is drawn
off and saved. It is usual to add sufficient water (for this purpose) to make the re-
maining acid of a gravity of about 50° B. The sludge oil is then purified by repeated
washings with water until the acid remaining in it is removed. For this purpose
equal volumes of water and sludge oil may be used, but the washing can be best
effected by the use of a larger quantity of water. The traces of acid in the
remaining oil are then neutralized by quick lime or caustic soda. The purified

page_text: oil has a strong and somewhat disagreeablc odour, and contains about ten per cent.
of volatile oils, which are converted into a hard resin with difficulty. To remove
these volatile substances sludge oil thus purified is introduced into a still with the
addition of from two to four per cent. of caustic soda, or caustic soda and about two
per cent. of the oxides of lead or manganese in order to oxidize any sulphur in the oil
and combine with it. Steam is then blown through the oil, the oil being kept hot (to
produce the distillation) either by a fire under the still or by the use of steam heated
to the required temperature, between 212° Fahrenheit and 450° Fahrenheit. The
action of the steam is continued until no more volatile oils are removed (generally
from five to ten hours), the steam is then shut off and the contents of the still
allowed to settle, when a sediment of tarry impurities and soda subsides, from
which the pure oil may be drawn off. The oil is then introduced into a still
or tank and oxidized by blowing currents of air through it, the oil being kept at a
temperature of from two hundred degrees Fahrenheit to four hundred and fifty
degrees Fahrenheit, either by means of a slow fire under the still, or by a steam
coil in the bottom of the tank, or by heating the air in a hot blast oven or otherwise
to the proper temperaturo before it is blown through the oil. The action of the air
is continued until a sample taken from the contents of the converting vessel is (on
cooling) found to be a resinous substance of a greater or less hardiness or consistency
as may be required for the particular purpose to which it is to be applied. And
after letting the contents of the still settle the hot resin is drawn off from the
sediment of impurities. The time required to effect the oxidation of the sludge
oil varies with the working temperature and with the extent of surface of oil
brought in contact with the air. It may be defined as between one and six days
generally, but by excessive use of air under high temperature the time may be
shortened to even less than one day. An inferior quality of this resinous substance
may be produced by treating the washed sludge oil in a still with caustic soda, and
blowing a current of air through it at about a temperature of four hundred degrees
Fahrenheit, which at the same time oxidizes the oil and removes the more volatile
portions which are distilled off until the residue is converted into a resinous
substance of the required hardness. This process last mentioned requires from two
to six days, but the resin produced is of a darker color than that made by first
treating it with steam and then with air at a lower temperature, as the coloring
matter is not affected by steam at five hundred degrees, while air at that tempera-
ture rapidly darkens it by oxidation. Sunlight bleaches the color of sludge oil, and
at the same time greatly accelerates the absorption of oxygen from the air. To
produce the lightest colored resins the sludge oil is steamed with five per cent. of
soda, 20° B, at a lower temperature about two hundred degrees to three hundred
degrees Fahrenheit for ten hours to remove the more volatile portions, and is then
oxidized and bleached by exposing the oil in shallow tanks covered by glass to the
sunlight, the oil being kept hot and fluid by steam coil in the bottom of the tank,
and currents of air are blown through it to produce the oxidation, the working
temperature in this case should not exceed three hundred degrees Fahrenheit.
Inferior qualities of sludge oil, such as those produced in the purification of lubri-
cating oils, and which contain a large quantity of tarry substances, are treated as
follows: The oil is charged into a still, and caustic soda and black oxide of man-
ganese (in the proportion of about five per cent. of soda and two per cent. of
manganese) are added, and the charge is distilled by a current of steam blown
through the oil assisted by a fire under the still until only tar and coke remain
behind. The distillation commences at about three hundred and fifty degrees i
Fahrenheit, and the fire being increased, the temperature in the still gradually rises
to about eight hundred degrees, when only the thick pitch remains in the still. By
the use of steam under pressure (especially when superheated) the oil can be
distilled with scarcely any decomposition, and the distillate which is of a yellow or
light red color can be converted into a superior light colored resinous substance by
oxidizing it with currents of air at the lowest possible working temperature. The
resin produced by this oxidation of sludge oil is distinguished from all other known

page_text: resins and resinous substances whatsoever by its behaviour with different chemicals
and solvents. It varies in color from yellow to dark garnet red according to the
method of its production. It is hard, brittle, and nearly odourless at ordinary
temperatures when oxidized as completely and thoroughly as possible. It is taste-
less, insoluble in and not acted upon by water, caustic soda, potassia, or ammonia
even when heated, alcohol of ninety per cent. dissolves but small quantities of this
resin color when boiled with it. It may be considered practically insoluble in
alcohol. Petroleum naphtha dissolves it very rapidly without the aid of heat,
spirits of turpentine readily dissolve it, especially on warming, ether, benzole,
chloroform, and bi-sulphide of carbon all dissolve the resin, a mixture of ether
and alcohol in the proportion of two parts of ether and one part of alcohol quite
readily dissolves this resinous substance, but not so readily as pure ether; linseed
oil and olive oil dissolve the resin when heated with it; concentrated sulphuric
acid dissolves it completely. The resin separates again on adding water, nitric acid
attacks it violently, and converts it into a brown tarry or gummy substance, having
a pleasant poculiar odour; hydrocholoric acid seeins to have little or no action on it.
It is well known that it has been proposed to use sludge oil as a paint oil, but
this has not been attended with practical success. I do not mean to be understood
however as making claim broadly to a process for freeing sludge oil from the acid
by the use of water and caustic alkalies, or by still further purifying it by subjec-
ting it to distillation, or by blowing steam through it for the purpose of removing
impurities, all of which it is well known have been practised since the discovery
of the present process of refining petroleum.
A new and useful varnish can also be produced from the resinous substance before
described in the following manner :-Dissolve or mix it (either with or without the
aid of heat) with such solvents as will completely and perfectly dissolve the resinous
substance and produce a useful varnish.
It has been found by experience and trial that petroleum naphtha readily dis-
solves the resinous substance in the cold, but botter by the aid of heat, by this
means producing an excellent varnish; also that spirits of turpentine completely
dissolve the resinous substance (especially when aided by heat), and produces a
varnish useful for many purposes, and that benzol and coal tar naphtha also quickly
dissolve the resinous substance and produco a varnish similar to the above. It has
also been found that linseed oil and other drying oils dissolve the resinous substance
readily when aided by heat, forming slow drying oil varnishes, and that a mixture
of drying oil and spirits of turpentine or drying oil and petroleum naphtha quickly
dissolve the resinous substance, and by this means forming a more or less quickly
drying oil varnish as the proportions of the ingredients are changed.
In the manufacture of varnish from the resinous substance referred to the pro-
portions of the resin, and of the different solvents will be determined by the use to
which the varnish is to be put, and the desired consistency of the resulting varnish.
By employing a greater or less quantity of solvents and oils the varnish can be
made thick or thin, and also be made to dry with more or less rapidity.
It has been found by experiment that a mixture in the following proportions
will make an excellent varnish which will dry very quickly. Resinous substance,
four pounds, petroleum naphtha, one gallon. Dissolve cold. Also that a good oil
varnish may be made by the following mixture:-Resinous substance, three pounds,
petroleum naphtha, one half gallon, linseed oil, one half gallon. Dissolve by the
aid of a moderate heat. For the petroleum naphtha one half-gallon of oil of
turpentine may be substituted advantageously. For waterproofing paper, the fol-
lowing proportions are best, resinous substance, three pounds, oil of turpentine, one
gallon. Dissolve by aid of a moderate heat.
The varnish manufactured as above may be distinguished from other varnishes
by the following properties and characteristics:-That on agitation of a sample of
the varnish with half its bulk of concentrated sulphuric acid the resinous substance
is separated by the acid, and the solvent rises clear to the surface of the acid. By

page_text: the appearance of the surface of wood or metal coated with this varnish enabling
a practised eye to distinguish it from other varnishes. By the solubility of the
varnish after drying in different chemical solvents it is distinguished from all other
varnishes whatsoever. The varnish after being evaporated to a hard residue, is
soluble in ether, benzol, bi-sulphide of carbon, spirits of turpentine, petroleum and
coal tar naphtha, chloroform, fusel oil, olive oil, linseed oil, and mixtures of two
parts of ether and one part of alcohol. It is scarcely dissolved by alcohol of ninety
per cent. even on boiling, except in minute quantities, and may be considered to
be insoluble in this liquid. Caustic alkalies have no effect upon it even on heating,
thereby distinguishing it from many natural resins.
It has also been discovered that the resinous substances derived from sludge oil by
other processes may be combined with raw or vulcanized india-rubber in all proportions
from one part of resin to twenty parts of rubber to one part of rubber in twenty parts
of resin, thereby producing a new and useful compound. The compound is made by
heating in an iron, steel, or other suitable vessel the resin derived from sludge oil until
it is completely melted, and then adding the rubber to it in small pieces, the heat
being kept sufficiently high to melt both rubber and resin, and thoroughly to
incorporate them. The india-rubber employed may be in the crude raw form as
imported, or rubber after it has been vulcanized may be used. But on account of
cheapness, I prefer to use old scrap rubber, such as worn out rubber, shoes, boots,
car springs, and also okl rubber hose, and other similar forms in which rubber is
used in the arts.
Other
The scrap rubber is introduced into the still through a manhole and stirred into
the melted resin. The plate of the manhole is then put on, and the heat raised
until a complete solution of the rubber is effected by the hot resiu. The manhole
plate is then removed, and any cloth or other similar material contained in the
scrap rubber is drawn out of the still by a rake or other similar means.
impurities and substances found in scrap rubber, such as lime, white lead, powdered
minerals, or dirt, are allowed to settle out by letting the contents of the still
remain at rest for some time, the mixture being kept fluid by heat. The new
resinous compound is then drawn off from the sediment and cast in any desired
form.
The degree of heat necessary to effect the above solution of the rubber in the
hot melted resin varies with the degree of vulcanization of the rubber employed;
it may be defined as between two hundred and fifty degrees Fahrenheit and six
hundred degrees Fahrenheit.
The uses to which this new manufacture or resinous substance can be put are
various. It may be used as a cement or employed otherwise in its solid state in
the arts.
To produce a japan varnish, the new resinous substance is dissolved in heavy
petroleum naphtha (about 50° Beaume) or other suitable solvent, and applied in
a thick coat to the goods or tin plates, which are subsequently baked in an oven
for a number of hours to render the film of varnish hard and permanent. The
temperature of the oven should be kept below five hundred degrees Fahrenheit,
or the compound undergoes decomposition. To japan in this manner; the com-
pound forming the base of the varnish should contain from ten to forty per cent.
of rubber. For a quick drying japan varnish to be used without subsequent
baking the compound is dissolved in light petroleum naphtha (about 75° Beaumé),
and for this purpose the compound forming the base of the varnish should contain
from five to twenty per cent. of rubbers.
The following is the receipt which it is preferred to use for a baking japan
varnish. Resin, three pounds, linseed oil, one half gallon, naphtha, one half
gallon.
For the purpose of waterproofing fabrics of cloth or paper, or utensils or vessels
made of the same, as paper pails, barrels, &c., the compound employed should
contain from ten to fifty per cent. of rubber. The varnish for this purpose is made
by dissolving from one to three pounds of the new compound in petroleum naphtha

page_text: or other suitable solvent. The thinner the varnish the more it will penetrate the
surface of the paper or fabric. A thick varnish remains on the surface after drying,
as a shining coat of resin.
For protecting iron and iron manufactures from the weather, as wire cables,
iron water pipes, ornamental castings, and analogous articles, this new com-
pound may be employed dissolved in naphtha or linseed oil, and may, if desired,
be colored black by a mixture of lamp-black and Prussian blue in suitable por-
tions. In preparing the new resinous substance or compound for this purpose
black and inferior grades of rubber scrap may be used.
Sludgo oil resin may be mixed with fifty to ninety per cent. of rubber as an
adulteration by melting or incorporating them together, and the resulting new
compound may be used for the manufacture of hard rubber goods of various
descriptions. For certain purposes the same effect may be produced in part by
dissolving the rubber in some suitable solvent, and mixing the resin desired from
sludge oil with it without the aid of heat, thus making a varnish directly from
these ingredients without the aid of heat; but it is preferred to first dissolve
the rubber in hot resin, and then dissolve the resulting new compound in naphtha,
oil of turpentine, or other suitable solvents.
Vulcanized rubber will not dissolve (to any appreciable extent) in petroleum
naphtha, but if it be first melted in hot resin the new compound can be easily
dissolved in naphtha.
The character of this new resinous compound or manufacture varies with the
proportions of its ingredients, with a large proportion of rubber, as fifty or more
per cent. The substance somewhat resembles vulcanized rubber in properties and
appearance, but with a small proportion of rubber as five to ten per cent., the
color and appearance of the sludge oil resin are unchanged, but the adhesiveness and
tougliness are greatly increased.
Chemically examined, the new substance has the properties of sludge-oil, resin,
and also of rubber. It is tasteless, odourless, or with a faint odour of rubber, is
not attacked by the alkalies and weaker acids, but is attacked by boiling with
strong sulphuric or nitric acids.
The new compound is soluble in those solvents which dissolve both the sludge
oil resin and rubber, as petroleum naphtha, benzole, oil of turpentine, &c.
What I wish to claim as new in the above described Invention, and desire to
secure by Letters Patent is-
First. The process herein described for oxidizing sludge oil or other substantially
equivalent substance by combining the oxygen of the air with sludge oil with the
aid and assistance of a moderate degree of heat, substantially as herein-before
described, for the purpose of producing a substance or manufacture possessing the
properties or qualities substantially as described. And this I claim, whether the
oxygen employed be derived from the air, or be otherwise derived, for the purposes
herein set forth, and whether the sludge oil be or be not mixed with other ingredients
as herein set forth.
Second. I claim the new manufacture or substance herein above described, and
possessing the substantial properties herein described, composed of sludge oil or
other substantially equivalent substance and oxygen chemically united together
as a solid substance of greater or less consistency or hardness as herein set forth.
And this I claim, whether other ingredients be or be not used in the production
of the said new manufacture or resinous substance lierein described.
Third. I claim the new varnish above described, and possessing the substantial
properties herein described, and composed of the resinous substance produced by
the oxidation of sludge oil or other substantially equivalent substance as above
described, dissolved and incorporated with naphtha and other suitable solvents
and oils as herein-above described and set forth. And this I claim, whether other
ingredients or substances or solvents be or be not used in the said manufacture as
herein-above described.

page_text: Fourth. I claim the new resinous compound or manufacture herein described,
and possessing the substantial properties herein described, composed of the resinous
substance derived from sludge oil and india-rubber incorporated together, sub-
stantially as and for the purposes herein set forth and described.
In witness whereof, I, the said William Edward Newton, have hereunto set
my hand and seal, the Twenty-sixth day of October, in the year of our
Lord One thousand eight hundred and seventy-six.
W. E. NEWTON. (LS.)