IMPROVEMENTS IN TREATING SLUDGE OIL WITH SULPHURIC ACID, AND THE PRODUCT ARISING THEREFROM, AND IN MANUFACTURING PAINTS OR VARNISHES THEREFROM."
Year: 1877

page_text: "
LETTERS PATENT to Henry Edward Newton, of the Office for Patents, 66,
Chancery Lane, in the County of Middlesex, Civil Engineer, for the Invention
of IMPROVEMENTS IN TREATING SLUDGE OIL WITH SULPHURIC ACID, AND
THE PRODUCT ARISING THEREFROM, AND IN MANUFACTURING PAINTS OR
VARNISHES THEREFROM." A communication from abroad by Walter Proctor
Jenney, of Brooklyn, in the State of New York, United States of America.
Sealed the 13th November 1877, and dated the 17th May 1877.
"
PROVISIONAL SPECIFICATION left by the said Henry Edward Newton at the
Office of the Commissioners of Patents on the 17th May 1877.
HENRY EDWARD NEWTON, of the Office for Patents, GG, Chancery Lanc, in the
County of Middlesex, Civil Engineer. "IMPROVEMENTS IN TREATING SLUDGE OIL
WITH SULPHURIC ACID, AND THE PRODUCT ARISING THEREFROM, AND IN MANU-
FACTURING PAINTS OR VARNISHES THEREFROM." A communication from abroad
by Walter Proctor Jenney, of Brooklyn, in the State of New York, United States of
America.
On the 3rd June, 1876, Letters Patent of Great Britain, Number 2330, were
granted to William Edward Newton, as a communication from the Inventor of the
present improvements for a process of treating sludge oil, whereby the oxidation was
effected by the use or agency of air, and for the products resulting from said process,
and for certain compounds of said products.
The present Invention consists in part of a new process of treating "sludge" and
sludge oil," the substance derived from sludge, whereby may be manufactured at
will either the new fluid substance partially oxidized sludge oil, hereafter described,
or by a more complete oxidation a solid resinous substance; and in part, of the new
manufacture or fluid oxidized sludge oil produced by the said new process when the
oxidation of the sludge oil is stopped or arrested, as hereafter set forth.
The mode of practising this Invention is as follows:-The sludge sometimes
contains illuminating oil, or other free and uncombined oils mixed with it, arising
from a want of care on the part of the refiner in drawing off the sludge from
the agitator. These uncombined. oils being less easily oxidized than sludge oil

page_text: interfere with the subsequent steps of the process, and contaminate the final product.
To remove these objectionable oils when found to be present in considerable quan-
tities the sludge is introduced into a lead-lined tank, and stirred or agitated with
about five per cent. by volume of petroleum naphtha (gravity, 60 to 70° Beaumé).
The naphtha disolves these oils, and rising to the surface is drawn off and removed
after allowing the heavier sludge time to subside to the bottom of the tank.
When only traces of uncombined oils are present in the sludge, this washing with
naphtha may be dispensed with. The sludge is next gently heated, care being
taken that the heat does not become too great and injure the product.
The sulphuric acid contained in the sludge acts upon the sludge oil combined or
dissolved in said acid, a portion of the sulphuric acid being decomposed into
sulphurous acid gas, which escapes, and oxygen, which unites with the sludge
oil.
The sludge is kept at as nearly a uniform and constant temperature as possible,
and the heating is continued until samples on testing show that the action of
oxidation has proceeded far enough to produce in the final product the degree of
hardness or fluidity which is desired for the particular purpose to which the product
is to be applied.
This test to determine the degree of oxidation of the sludge oil is made as
follows: A sample of the sludge is taken from the contents of the tank, and
decomposed by the addition of an equal volume of water; the resulting sludge oil
floats on the surface of the heavy and hot mixture of acid and water, but, on removing
the sludge oil and placing it in pure water at the common temperature, the oil sinks
in the water if it be oxidized sufficiently to produce in the final steps of the process
a solid resinous substance described in the above-mentioned Patent. It has been
found however by experience that for certain purposes it is best to arrest this
oxidation of the sludge oil, so that the final product shall be a fluid substance of
greater or less viscidity or consistency; and to do this the action of the sulphuric
acid upon the sludge oil is stopped at a point where by the above test the sludge
oil, although partially oxidized, will still float upon the surface of pure water.
This action of sulphuric acid upon the combined sludge oil may assisted by
the addition of other oxidizing agents, as five per cent. of oxide of manganese, the
manganates of the alkalies, bichromate of potassa, chlorato of potassa, nitric and
chromic acids, but the employinent of such substances requires great care in this
process.
After the action of the acid upon the sludge oil has been maintained for a suffi-
ciently long time, the sludge is decomposed by the addition of water, enough water
being added to reduce the gravity of the sulphuric acid to about 50° Beaumé. After
allowing the acid to subside to the bottom of the tank it is drawn off from the
sludge oil, and used in the manufacture of superphosphates, or it is renovated and
reconcentrated by the processes now in general use.
The oxidized sludge oil is in many cases so thick and viscid as to be difficult to wash
or purify. To obviate this, petroleum naphtha (gravity, 60° to 70° Beaumé) is added,
a little at a time, to the oxidized sludge oil, and mixed or stirred with it, the solution
of the oil in the naphtha being aided by applied heat. The addition of the naphtha
is continued until the solution is thin and fluid, so as to be readily washed in
the subsequent steps of the process. For this purpose from one to ten barrels
of naphtha may be added to ten barrels of oxidized sludge oil to effect
its solution, the quantity of the naphtha varying with the consistency or degree of
oxidation of the oil. When the sludge oil has been only partially oxidized in the
preceding operation it is often so fluid that when heated to 212° Fabr. it can readily
be washed and purified without thinning with naphtha, and in this case the use of
naphtha may be dispensed with.
The oxidized sludge oil, or the solution of the oxidized sludge oil in naphtha, is
then removed to a lead-lined tank provided with a close fitting cover and a con-
densing worin, so that any naphtha or light oils distilling off owing to the heat of
the steam and water may be condensed and saved.

page_text: Hot water is showered upon the surface of the oxidized sludge oil, and steam
is blown through it to agitate and mix the oxidized sludge oil with the hot.
water.
The water rapidly removes the sulphuric acid mechanically mixed and held in
suspension in the oxidized sludge oil or naphtha solution, and from time to time the
washings are drawn off by a waste pipe at the bottom of the tank. The water
washing is continued until the water flowing from the waste pipe no longer tastes
of acid or shows its presence in any considerable quantity by the usual chemical
tests. The contents of the tank are then allowed to remain at rest to separate tho
excess of water held in suspension; the water is drawn off as completely as practicable,
and about 5 per cent. by volume of a solution of caustic soda (gravity, 25° Beaumé)
is added and agitated with the oxidized sludge oil or naphtha solution by plunging
steam through it to neutralize and remove any remaining traces of acid. A small
quantity of aminonia may be added advantageously to the soda solution, and a
cheaper but less convenient alkaline liquid may be obtained by using milk of lime.
After agitation with the alkali the contents of the tank are allowed to remain at
rest to separate the alkali as completely as possible from the purified oil. The
purified oxidized sludge oil contains from 10 to 30 per cent. of light volatile
oils mixed with it as well as the naphtha which may have been added to increase its
fluidity. To remove these volatile oils and the naphtha the oxidized sludge oil is
introduced into a still and heated, and to further purify the oxidized sludgo oil or
increase its drying property from one to five per cent. of oxide of lead or manganese
or five per cent. of a solution of caustic soda (gravity, 25° Beaumé) may be added
to the contents of the still.
The heat of the still is gradually raised until the water remaining in the oxidized
sludge oil is removed, and the naphtha and volatile oils are distilled off.
The product resulting from this distillation varies in hardness or fluidity with
the degree of oxidation of the sludge oil effected in the preceding operation of
oxidation by the sulphuric acid. If, as here before mentioned, the oxidation has
been carried to the production of a thick viscid oil, which will sink in pure water,
the product remaining after the distillation of the naphtha and volatile oils is at
ordinary temperature a solid substance, substantially the same as the resinous
substance described in the Specification of the Patent before referred to; but when
the oxidation has been stopped, as herein-before described, and the sludge oil floats on
water, the product of the distillation is a fluid substance at ordinary tempera-
tures of greater or less consistency or viscidity, and distinguished from the solid
oxidized sludge oil in being less oxidized, in having a much lower melting point, in
being somewhat more readily soluble in the different solvents, and in drying much
more slowly to a hard substance.
When desired this new fluid substance, partially oxidized sludge oil, may bo
combined with india-rubber, or it may be made into a varnish by dissolving it with
naphtha or other suitable solvents.
The following modification of this process may be sometimes employed:-The
sludge oil is taken directly from the manufacturer of superphosphates in the form
in which it is at present usually thrown away, containing mechanically mixed with
it a considerable quantity of sulphuric acid (gravity, about 50° Beaumé), which it is
not worth while for the manufacturer to take the trouble to separate. This impure
sludge oil is treated as follows:-It is introduced into a lead-lined tank, and gently
heated to a temperature not exceeding 212 Fahr., which is maintained until the
acid mixed with it has effected the requisite oxidation. This operation resembles
that above described, but owing to the less quantity of acid and its lower gravity
the action is not as rapid as in the case of sludge, but this can be obviated by working
at a slightly higher temperature.
The action of the sulphuric acid may be assisted by the addition of oxidizing
agents, as before explained.
When the oxidation of the sludge oil has proceeded as far as is desired, the same
tests being used as in the case of sludge to determine the degree of the oxidation, tho

page_text: with a vehicle composed wholly or in part of oxidized sludge oil dissolved by or
incorporated with naphtha or other suitable solvent.
In preparing the above-mentioned vehicle it is preferred to use the fluid substance,
partially oxidized sludge oil, where a slow drying and strongly adhesive vehicle is
desired, and to employ the solid resinous substance or more completely oxidized
sludge oil where the object is to produce a quickly drying vehicle, and to impart to
the paint made with it this desirable quality, the object being to produce a vehicle
having about the consistency of boiled linseed oil; for the solvent it is preferred to
employ petroleum naphtha (gravity, 60° to 70° Beaume) on account of its cheap-
ness and quickly drying property, using nearly the following proportions to make
one gallon of vehicle:-
Solid or fluid oxidized sludge oil, 3 to 4 pounds.
Naphtha, 2 to 21/2 quarts.
To be dissolved with or without the use of heat.
Where a paint is, required which shall strongly adhere to the surface, and resist
wearing and abrasion, a compound of india-rubber and sludge oil may be employed
as the base for the vehicle.
In some cases it is preferred to use a vehicle, the base of which is oxidized sludge
oil inelted or incorporated with ten to forty per cent. of tallow, grease, fatty acids,
paraffine, or other equivalent substance. In order that the tallow or grease may
dry or harden readily it is mixed or boiled with oxide of lead or oxide of zinc, using
one ounce of oxide to each pound of tallow; in the case of paraffine this addition
of oxide of lead or zinc is unnecessary. The tallow or paraffine is added to the
oxidized sludge oil, and melted and stirred with it. Three and one-half pounds of
the compound are dissolved in two and one-half quarts of naphtha to form a gallon
of vehicle.
Other substances, as asphaltes, bitumen, coal tar, wood tar, rosin, pitch, the residuum
from petroleum distillation, animal fats or oils, vegetable oils or gums may be added
to the above-described vehicle, but such additions are not necessary to the production
of a suitable vehicle.
To prepare a paint for coating the bottom of wooden vessels which shall preserve
the wood from decay and the attacks of marine worms, as well as keep the surface
from fouling, there is ground or mixed with any of the above described vehicles a suffi-
cient quantity of any finely divided solid substance, containing copper or compound
or salt of copper that will afford the desired protection, and by the gradual corrosion
or solution of the copper, by the action of the water will produce a poisonous action
destructive to all forms of life coming in contact with it.
In preparing a paint for the bottom of iron vessels the following mixtures may
be employed, viz. :-
Red lead, five to ten pounds.
Vehicle in any of the above mentioned forms, one gallon,―
To be ground together in a paint mill as fine as practicable.
Red lead, five pounds.
White zinc, three pounds.
Vehicle in any of the above mentioned forms, one gallon.
For the red lead in the above mixtures an equal weight of oxides of iron ground
fine, known as "Prince's metallic," may be substituted, forming a cheaper paint.
This thick varnish, made from oxidized sludge oil, suits admirably for coating the
bottom of yachts and pleasure boats where great speed is desired, the smooth surface
formed by the varnish greatly decreasing the resistance of the water to the boat's
progress. For this purpose two coats of varnish applied upon the bare wood or over
the surface of other paint may be employed.
A compound well adapted for coating the bottoms of vessels, and forming a pro-

page_text: tecting surface over other paint, may be made by melting or incorporating tallow,
fatty acids, grease, paraffine, or equivalent substance with oxidized sludge oil, using
from one-fourth to one pound of tallow to cach pound of oxidized sludge oil. To
cach pound of this compound of tallow and oxidized sludge oil from one-half
to one pound of litharge, red lead, or oxide of zinc may be added with advan-
tage. This compound may be melted and applied with brushes while hot and fluid,
or it may be dissolved or incorporated with naphtha or other suitable solvent, and
applied in the usual manner to the bottoms of vessels.
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Henry Edward Newton in the Great Seal Patent Office on tlie 17th
November 1877.
"
HENRY EDWARD NEWTON, of the Office for Patents, 66, Chancery Lanc, in the
County of Middlesex, Civil Engineer. IMPROVEMENTS IN TREATING SLUDGE OIL
WITH SULPHURIC ACID, AND THE PRODUCTS ARISING THEREFROM, AND IN MANU-
FACTURING PAINTS OR VARNISHES THEREFROM." A communication from abroad by
Walter Proctor Jenney, of Brooklyn, in the State of New York, United States of
America.
In the purification of hydrocarbon oils produced by the distillation of crude
petroleum, asphaltes, or bitumens, or by the destructive distillation of coal, resins,
or bitumenous shales, the oils are agitated with two per cent. or more of concentrated
sulphuric acid (66° Beaumé, 186 specific gravity) 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 red 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 hydrocarbon oils, 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, producing a weaker acid
(about 50° Beaumé) used in the manufacture of superphosphate of lime, and 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."
On the Third of June 1876 Letters Patent of Great Britain, No. 2339, were granted
to William Edward Newton as a communication from the Inventor of the present
improvements for a process of treating sludge oil, whereby the oxidation was effected
by the use or agency of air, and for the products resulting from said process, and
for certain compounds of said products.
The present Invention consists in part of a new process of treating "sludge" and
sludge oil," the substances derived from sludge, whereby may be manufactured at
will, either the new fluid substance, partially oxidized sludge oil hereafter described,.
or by a more complete oxidation, a solid resinous substance. And in part of the

page_text: new manufacture or fluid oxidized sludge oil produced by the said new process, when
the oxidation of the sludge oil is stopped or arrested, as hereafter set forth.
The mode of carrying out the Invention is as follows:-The sludge sometimes
contains illuminating oil or other free and uncombined oils mixed with it, arising
from a want of care on the part of the refiner in drawing off the sludge from the
agitator. These uncombined oils, being less easily oxidized than sludge oil, interfere
with the subsequent steps of the process and contaminate the final product. To
remove these objectionable oils when found to be present in considerable quantities,
the sludge is introduced into a lead-lined tank, and stirred or agitated with about
five per cent. by volume of petroleum naphtha (gravity 60 to 70° Beaumé), the
naphtha dissolves these oils, and, rising to the surface, is drawn off and removed,
after allowing the heavier sludge to subside to the bottom of the tank.
When only traces of uncombined oils are present in the sludge this washing with
naphtha may be dispensed with. The sludge is next gently heated by a steam coil
in the bottom of the tank, or in other suitable manner, care being taken by observ-
ing the indications of thermometers placed in different parts of the tank that the
heat does not become too great and injure the product.
The sulphuric acid contained in the sludge acts upon the sludge oil combined or
dissolved in the said acid, a portion of the sulphuric acid being decomposed into
sulphurous acid gas, which escapes, and oxygen which unites with the sludge oil.
The temperature of the sludge should in no case be allowed to exceed 212°
Fahrenheit, or the acid will act so violently upon the sludge oil combined or dissolved
in it that the product will be difficultly soluble in naplitha, and not so well adapted
to the purposes to which it is proposed to apply it. I may define the proper work-
ing temperature as between 75° Fahrenheit and 150° Fahrenheit; at the latter
temperature the action is quite rapid, and a brisk effervescence of sulphurous acid
gas may be observed to take place. The length of time required to complete the
action of the sulphuric acid on the combined oil varies greatly with different
samples of sludge; with the working temperature and the degree of oxidation
required in the final product, the higher the temperature the more rapid the action.
I may define the time required as from twelve hours to forty-eight hours, though in
some cases the length of time may be less or even greater than this.
The sludge is kept at as nearly a uniform and constant temperature as possible,
and the heating is continued until samples on testing shew that the action of
oxidation has proceeded far enough to produce in the final product the degree of
hardness or fluidity which is desired for the particular purpose to which the product
is to be applied.
"
This test to determine the degree of oxidation of the sludge oil is made as
follows: A sample of the sludge is taken from the contents of the tank and
decomposed by the addition of an equal volume of water; the resulting sludge oil
floats on the surface of the heavy and hot mixture of acid and water, but on
removing the sludge oil and placing it in pure water at the common temperature,
the oil sinks in the water, if it be oxidized sufficiently to produce in the final steps
of the process a solid resinous substance, described in English Letters Patent,
No. 2339 of 1876. I have found, however, by experience, that for certain purposes,
it is best to arrest this oxidation of the sludge oil, so that the final product shall be
a fluid substance of greater or less viscidity or consistency, and to do this, the action
of the sulphuric acid upon the sludge oil is stopped at a point where by the above
test the sludge oil, although partially oxidized, will still float on the surface of pure
water.
This action of sulphuric acid upon the combined sludge oil may be assisted by
the addition of other oxidizing agents, as five per cent. of oxide of manganese, the
manganates of the alkalies, bicarbonate of potassa, chlorate of pottassa, nitric and
chromic acids, but the employment of such substances requires great care in this
process.
After the action of the acid upon the sludge oil has been maintained for a suffi-

page_text: cicutly long time, the sludge is decomposed by the addition of water, enough water
being added to reduce the gravity of the sulphuric acid to about 50° Beaumé.
After allowing the acid to subside to the bottom of the tank, it is drawn off from
the sludge oil and used in the manufacture of superphosphates, or it is renovated
and re-concentrated by the processes now in general use.
The oxidized sludge oil is in many cases so thick and viscid as to be difficult to
wash or purify. To obviate this, petroleum-naphtha (gravity, 60° to 70° Beaumé)
is added, a little at a time, to the oxidized sludge oil, and mixed or stirred with it,
the solution of the oil in the naphtha being aided by heat from the steam coil in the
bottom of the tank. The addition of the naphtha is continued until the solution is
thin and fluid, so as to be readily washed in the subsequent steps of the process;
for this purpose, from one to ten barrels of naphtha may be added to ten barrels of
oxidized sludge oil to effect its solution, the quantity of the naphtha varying with
the consistency or degree of oxidation of the oil. When the sludge oil has been
only partially oxidized in the preceeding operation it is often so fluid that, when
heated to 212° Fahrenheit, it can readily be washed and purified without thinning
with naphtha, and in this case the use of naphtha may be dispensed with,
The oxidized sludge oil, or the solution of the oxidized sludge oil in naphtha, is
then removed to a lead-lined tank, provided with a close-fitting cover and a con-
densing worm, so that any naphtha or light oils distilling off owing to the heat of
the steam and water may be condensed and saved.
Hot water is showered upon the surface of the oxidized sludge oil, and steam
is blown through it to agitate and mix the oxidized sludge oil with the hot
water.
The water rapidly removes the sulphuric acid mechanically mixed and held in
suspension in the oxidized sludge oil or naphtha solution, and from time to time
the washings are drawn off by a waste pipe at the bottom of the tank. The water
washing is continued until the water flowing from the waste pipe no longer tastes
of acid or shews its presence in any considerable quantity by the usual chemical
tests. The contents of the tank are then allowed to remain at rest, say, for twelve
hours, to separate the excess of water held in suspension; the water is drawn off
as completely as practicable, and about five per cent., by volume, of a solution of
caustic soda (gravity, 25° Beaume) is added and agitated with the oxidized sludge
oil or naphtha solution by plunging steam through it to neutralize and remove any
remaining traces of acid. A small quantity of ammonia may be added advan-
tageously to the soda solution; and a cheaper, but less convenient, alkaline liquid
may be obtained by using milk of lime. After agitation with the alkali, the
contents of the tank are allowed to remain at rest for twenty-four hours, to separate
the alkali as completely as possible from the purified oil. The purified oxidized.
sludge oil contains from ten to thirty per cent. of light volatile oils mixed with it,
as well as the naphtha, which may have been added, to increase its fluidity; to
remove these volatile oils and the naphtha, the oxidized sludge oil is introduced
into a still or other suitable vesssel, and heat is gradually applied, either by a steam
coil inside the still, or, more advantageously, by a fire built underneath it, and, to
'further purify the oxidized sludge oil, or increase its drying property, from one to
five per cent. of oxide of lead or manganese, or five per cent. of a solution of
caustic soda (gravity, 25° Beaume) may be added to the contents of the still.
The heat of the still is gradually raised until the water remaining in the oxidized
sludge oil is removed, and the naphtha and volatile oils are distilled off; the distilla-
tion may be assisted by steam blown through the oil in the usual manner. The
temperature of the contents of the still may be raised to 400° Fahrenheit or even
500° Fahrenheit without injury to the product, but a lower temperature is usually
sufficient to effect this result. The time required for this distillation is about
twenty-four hours for a charge of twenty barrels of oil, the heat being continued
until the naphtha and volatile oils have been removed.
The product resulting from this distillation varies in hardness or fluidity with the
degree of oxidation of the sludge oil, effected in the preceding operation of oxida

page_text: tion by the sulphuric acid. If, as heretofore mentioned, the oxidation has been
carried to the production of a thick, viscid oil, which will sink in pure water, tho
product remaining after the distillation of the naphtha and volatile oils is, at
ordinary temperature, a solid substance, substantially the same as the resinous
substance described in the Specification of the Patent before referred to, Letters
Patent, Number 2339, of 1870. But when the oxidation has been stopped, as herein-
before described, and the sludge oil floats on water, the product of distillation is a
fluid substance at ordinary temperatures, of a greater or less consistency or viscidity,
and distinguished from solid oxidized sludge oil described in the Specification before
referred to, being less oxidized in having a much lower melting point, in being
soine what more readily soluble in the different solvents, and in drying much more
slowly to a hard substance. Like the solid resinous substance, alkalies have no
action on fluid oxidized sludge oil, except to slightly redden its color.
When desired, this new fluid substance partially oxidized sludge oil may be
combined with india-rubber, or it may be made into a varnish by dissolving it with
naphtha or other suitable solvents, as described in English Letters Patent, Number
2339 of 1876.
The following modification of this process may be sometimes employed:-The
sludge oil is taken directly from the inanufacturer of superphoshpates in the form
in which it is at present usually thrown away, containing, mechanically mixed with
it, a considerable quantity of sulphuric acid (gravity, about 50° Beaumé), which it
is not worth while for the manufacturer to take the trouble to separate. This
impure sludge oil is treated as follows:-It is introduced into a lead-lined tank, and
gently heated by a steam coil to a temperature not exceeding 212° Fahrenheit,
which is maintained for twenty-four to sixty hours, or until the acid mixed with it
has effected the requisite oxidation. This operation resembles that above described
in the oxidation of the sludge oil by the acid combined with it; but owing to the
less quantity of acid and its lower gravity, the action is not as rapid as in the case
of sludge; but this can be obviated by working at a slightly higher temperature.
The action of the sulphuric acid may be assisted by the addition of oxidizing
agents, such as five per cent. of oxide of manganese, the manganates of the
alkalies, bichromate of potassa, chromic acid, chlorate of potassa; but such
additions of oxidizing substances require care in their employment in this process. .
When the oxidation of the sludge oil has proceeded as far as is desired, the same
tests being used as in the case of sludge to determine the degree of the oxidation,
the oxidized sludge oil is thinned by naphtha, if necessary, and then purified by
washing and distillation, as above described.
In preparing a new paint, according to this Invention, finely-divided dry
pigments, such as earths, oxides, minerals, salts, compounds, metals, or alloys are
ground or mixed with a vehicle composed wholly or in part of oxidized sludge oil,
dissolved by or incorporated with naphtha or other suitable solvent.
In preparing the above-mentioned vehicle I prefer to use the fluid substance,
partially oxidized sludge oil, where a slow drying and strongly adhesive vehicle is
desired, and to employ the solid resinous substance or more completely oxidized
sludge oil, where the object is to produce a quickly drying vehicle and to impart to
the paint made with it this desirable quality, the object being to produce a vehicle
having about the consistency of boiled linseed oil; for the solvent it is preferred to
employ petroleum naphtha (gravity 60° to 70° Beaumé) on account of its cheapness
and quickly drying quality, using nearly the following proportions to make one
gallon of vehicle :-
Solid or fluid oxidized sludge oil, 3 to 4 lbs.
Naphtha, 2 to 21, quarts.
To be dissolved with or without the use of heat.
The vehicle may be varied in composition according to the particular use to which
it is to be applied, or the properties or qualities desired in the resulting paint.
Whero a paint is required which shall strongly adhere to the surface and resist
wearing and abrasion, a compound of india-rubber and sludge oil may be employed

page_text: as the base for the vehicle, as described in Patent 2339 of 1870. For this purpose
the rubber compound should contain from ten to thirty per cent. of india-rubber;
and to make one gallon of vehicle four pounds of the rubber compound or base
should be dissolved in two and one-half quarts of naphtha by the aid of heat.
This vehicle forms strongly adhesive paints when it contains twenty or thirty per
cent. of rubber, but the surface fouls more readily than paints formed of oxidized
sludge oil without rubber; and in some cases it is preferred to use a vehicle the
base of which is oxidized sludge oil, melted or incorporated with ten to forty per
cent. of tallow, grease, fatty acids, paraffine, or other equivalent substance. In order
that the tallow or grease may dry or harden readily, it is mixed or boiled with oxide
of lead or oxide of zinc, using one ounce of oxide to cach pound of tallow; in the case
of parafline this addition of oxide of lead or zinc is unnecessary.
The tallow or
paraffine is added to the oxidized sludge oil, and melted and stirred with it; threo
and one-half lbs. of the compound are dissolved in two and one-half quarts of naphtha
5 to form one gallon of vehicle.
Other substances, as asphaltes, bitumen, coal tar, wood tar, rosin, pitch, tho
residuum from petroleum distillation, animal fats or oils, vegetable oils or gums, may
be added to the above-described vehicle, but such additions are not necessary to the
production of a suitable vehicle.
To prepare a paint for coating the bottom of wooden vessels which shall preserve
the wood from decay and the attacks of marine worms, as well as keep the surface
from fouling, there is ground or mixed with any of the above-described vehicles a
sufficient quantity of any finely divided solid substance containing copper, or
compound, or salt of copper that will afford the desired protection, and by the
5 gradual corrosion or solution of the copper by the action of the water will produce
a poisonous action, destructive to all forinis of life coming in contact with it.
It is not intended to limit this Invention to the use of any special form or
compound of copper, but to employ the well-known pigments and substances
containing copper, both natural and artificial, which have heretofore been used in
O painting the bottoms of vessels.
The following mixtures may be used to produce a useful and very poisonous paint
suitable to the purposes above mentioned:
Dry verdigris, three to five pounds.
Vehicle in any of the above-described forms, one gallon.
To be mixed together and ground in a paint mill several times until a smooth
paint is produced.
Oxide of copper, six to nine pounds.
Vehicle in any of the above-described forins, one gallon.
Mixed by grinding as fine as practicable.
Finely divided metallic copper or alloy of copper, five to eight pounds.
Vehicle in any of the above forins, one gallon.
The bottom of the vessel having been scraped clean, the paint may be applied in
the usual manner, one or more coats being spread on as evenly as possible, and the
vessel launched into the water before the paint becomes perfectly hard.
On preparing a paint for the bottom of iron vessels the use of copper in any form
seems to be impracticable, owing to the galvanic action of the copper and the con-
sequent corrosion of the iron. The object in this case is to prepare a paint which
shall afford permanent protection to the iron from rust and corrosion, and at the
same time give a surface so sinooth that sea weeds or barnacles cannot readily become
attached or grow upon it. For this purpose the following mixtures may be
employed:-
Red lead, five to ten pounds.
Vehicle in any of the above-mentioned forms, one gallon.
To be ground together in a paint mill as fine as practicable, or,—
Red lead, five pounds.

page_text: For the red lead in the above mixtures an equal weight of oxides of iron, ground
fine, known as "Prince's metallic," may be substituted, forming a cheaper paint.
The bottom of the vessel having been scraped clean, two coats of the above-
described paint should be applied in the usual manner, and after they are perfectly
hard and dry the surface should be covered by two smooth coats of a varnish made
by dissolving six to eight pounds of oxidized sludge oil in one gallon of naphtha.
This protecting coat of pure oxidized sludge oil gives an extremely smooth gloss-like
surface, increasing the speed of the vessel, and at the same time affording no ready
attachment for grass or barnacles. This thick varnish, made from oxidized sludge
oil, suits admirably for coating the bottom of yachts and pleasure boats where great
speed is desired, the smooth surface formed by the varnish greatly decreasing the
resistance of the. water to the boat's progress. For this purpose two coats of
varnish, applied upon the bare wood or over the surface of the other paint may be
employed.
A compound well adapted for coating the bottoms of vessels and forming a
protecting surface over other paint may be made by melting or incorporating tallow,
fatty acids, grease, paraffine, or equivalent substance, with oxidized sludge oil,
using from one-fourth to one pound of tallow to each pound of oxidized sludge oil.
To each pound of this compound of tallow and oxidized sludge oil from one-half a
pound to one pound of litharge, red lead, or oxide of zinc, may be added with advan-
tage. This compound may be melted and applied with brushes while hot and fluid,
or it may be dissolved or incorporated with naphtha or other suitable solvent, and
applied in the usual manner to the bottoms of vessels.
Having now described the nature of this Invention for "Improvements in Treating
Sludge Oil with Sulphuric Acid, and the Products arising therefrom, and in Manu-
facturing Paints or Varnishes therefrom," and having explained the manner of
carrying the same into effect, as communicated to me by my foreign correspondent,
I wish it to be understood that under the above in part recited Letters Patent, I
claim,―
I. The process of manufacture herein described for producing from sludge or sludge
oil the manufacture or substance herein described, and possessing the properties or
qualities substantially as described, by oxidizing the sludge oil by sulphuric acid,
substantially as herein described and set forth.
II. The new substance or manufacture, herein described, being partially oxidized
fluid sludge oil, possessing the properties or qualities herein described.
III. The new manufacture or paint herein described, possessing substantially the
properties or qualities herein described, composed of a vehicle consisting in whole or
in part of oxidized sludge oil and a suitable solid substance or base, as hercin
described and set forth."
IV. The new manufacture or copper paint herein described, and possessing
substantially the qualities or properties herein described, composed of a vehicle con-
sisting in whole or in part of oxidized sludge oil and a suitable body containing
copper, as herein described and set forth.
In witness whereof the said Henry Edward Newton has hereunto set his hand
and seal, this 17th day of November, in the year of our Lord One thousand
eight hundred and seventy-seven.