A PROCESS FOR THE RECOVERY, PURIFICATION, AND REVIVIFICATION OF SULPHURIC ACID SPENT AND DETERIORATED IN THE RE- FINING OF PETROLEUM, COAL, AND SHALE OILS
Year: 1870

page_text: LETTERS PATENT to George Willoughby Hemans, of Victoria Street,
Westminster, in the County of Middlesex, Civil Engineer, for
the Invention of "A PROCESS FOR THE RECOVERY, PURIFICATION, AND
REVIVIFICATION OF SULPHURIC ACID SPENT AND DETERIORATED IN THE RE-
FINING OF PETROLEUM, COAL, AND SHALE OILS." -A communication from
abroad by Michael Barrett, M.D., of Toronto, Upper Canada.
Sealed the 11th November 1870, and dated the 16th May 1870.
PROVISIONAL SPECIFICATION left by the said George Willoughby
Hemans at the Office of the Commissioners of Patents, with his
Petition, on the 16th May 1870.
I, GEORGE WILLOUGHBY HEMANS, of Victoria Street, Westminster,
in the County of Middlesex, Civil Engineer, do hereby declare the
nature of the said Invention for "A PROCESS FOR THE RECOVERY, PURI-.
FICATION, AND REVIVIFICATION OF SULPHURIC ACID SPENT AND DETERIORATED
IN THE REFINING OF PETROLEUM, Coal, and SHALE OILS," to be as follows:-
This Invention has reference to the recovery, purification, and
revivification of the sulphuric acid spent and deteriorated in the process
:―
-

page_text: of refining petroleum, coal, and shale oils, by means of oxygen gas in the
nascent state. The spent and deteriorated acid as it comes from the
agitator is to be received in a lead-lined vessel and heated to 212 degrees
of Fahrenheit's thermometer, causing any oil that may have been drawn
off with the sulphuric acid to come to the surface; this oil is to be
removed. The spent acid in the same vessel is then to be heated with
finely powdered black oxide of manganese, in the proportion of half an
ounce of the manganese to one pound of acid and heat applied for six
hours by means of a steam jacket or otherwise, the effect being that the
oxygen gas evolved by the action of a portion of the sulphuric acid upon
the black oxide of manganese will combine with the bituminous or tarry
matter contained in the spent acid causing it to rise to the surface upon
cooling. The bituminous or tarry matter having been removed a
mixture of alumina and water has to be prepared by mixing one pound of
fuller's earth or pure clay with one gallon of water, of this mixture one
gallon is to be added to every ten gallons of the acid and the mixture
to be boiled. Upon cooling, any remaining bituminous or tarry matter
will have come to the surface and must be removed. In the course of
five hours the alumina will be precipitated together with all remaining
impurities and a clear liquid will be obtained. The clear liquid is to be
carefully drawn off from the aluminous sediment and concentrated by
any of the methods usually employed in the concentration of sulphuric
acid. The acid thus obtained is pure sulphuric acid and fitted for every
purpose to which sulphuric acid can be applied.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said George Willoughby Hemans in the Great Seal
Patent Office on the 16th November 1870.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, GEORGE
WILLOUGHBY HEMANS, of Victoria Strect, Westminster, in the County
of Middlesex, Civil Engineer, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Sixteenth day of May, in the year of
our Lord One thousand eight hundred and seventy, in the thirty-third
year of Her reign, did, for Herself, Her heirs and successors, give and
grant unto mc, the said George Willoughby Hemans, Her special

page_text: licence that I, the said George Willoughby Hemans, my executors,
administrators, and assigns, or such others as I, the said George
Willoughby Hemans, 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 law-
fully 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 "A PROCESS FOR THE RECOVERY, PURIFICATION, AND REVI-
VIFICATION OF SULPHURIC ACID SPENT AND DETERIORATED IN THE REFINING OF
PETROLEUM, COAL, AND SHALE OILS," a communication to me from abroad
by Michael Barrett, M.D., of Toronto, Upper Canada, upon the condition
(amongst others) that I, the said George Willoughby Hemans, my
executors or administrators, by an instrument in writing under my, or
their, or one of their hands and seals, should particularly describe and
ascertain the nature of the said Invention, and in what manner the
same was to be performed, and cause the same to be 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 George Willoughby Hemans, do
hereby declare the nature of my said Invention, and in what manner
the same is to be performed, to be particularly described and ascertained
in and by the following statement :—
This Invention has reference to the recovery, purification, and revivi-
fication of the sulphuric acid spent and deteriorated by means of oxygen
gas in a nascent state. This spent acid recovery process is conducted
as follows:-The slush or spent acid is placed in a vessel represented
in the Drawings which accompany these Presents, which I term the
separator, this I heat up with dry steam until a temperature of about
120 degrees Fahrenheit has been reached. Then I sprinkle in about
six or seven pounds of black oxide of manganese and turn on free steam.
I cover the tank over, but keep a sharp look out that it does not foam
over. Should it rise too high in the tank I turn off the steam for a short
time, when it will subside. I keep heating up for six or eight hours,
and then allow cooling to take place, and when cool I remove what tar
and oil has come to the surface, taking care that none is taken off,
except what is free from acid. When the hard asphaltum is reached I
pour on sufficient oil (about five or six gallons) (American measure,
as described below) to dissolve it, and heat up again until it is all soft,

page_text: and I remove the asphaltum in the shape of tar. Then I add, say, two
or three pounds of manganese and heat up again for about two hours.
removing what comes to the surface, and continue adding manganese
in small quantities, and heating up until nothing will come to the
surface (the whole quantity of manganese to be used is twelve and
a half pounds to the hundred gallons, by which I mean American
gallons, 833 of a British imperial gallon of spent acid). The acid
is then ready for the charring pan, and it must be run out of the tank
with great care in order not to disturb the sediment in the bottom when
in the charring pan. After this I proceed as quickly as possible to get
up the heat until 51 degrees Beaume are reached, when the heat must
be watched closely, as the acid is likely to foam over after reaching that
strength. I then skim off what comes to the surface and dump the
skimmings into the separator, so that any acid they may contain will be
worked up in the following batch while charring. Should the surface
of the pan become covered with scum it will very likely foam over, and
it should be one man's work (at this stage) to stand over the pan and
see that a portion of the surface is kept clear in order to prevent un-
necessary foaming over. After it has reached 53 degrees Beaume it
will foam over nearly all the time, and requires most faithful watching
(the foam is nearly all acid and should be saved by returning to the
separator). I continue to concentrate until 60 degrees Beaume is
reached, and if it can be accomplished it would be all the better to run
it up to 62 degrees Beaume, but not beyond that point, as it will then
cut the lead pan. When up to the required strength I allow the same
to cool in order to remove it into the alumina vat. Care must be taken
that it is not removed from the charring pan before the furnace is
cold, or otherwise the lead pan will melt. The pan having cooled, say,
to 200 degrees Fahrenheit the next stage is the alumina process. I run
in about as much clear cold water into the alumina vat as there is acid
in the charring pan, and I then dump the acid into the water. I take
everything out of charring pan, because any dirt that may be in it will
settle in the alumina vat. When all the acid has been placed in the
alumina vat I dilute it down to about 16 degrees Beaume with clear
cold water, taking care that the acid and water are evenly mixed (this
can be done by taking a copper skimmer and stirring well from the
bottom). Then I mix up about ten pounds of alumina to every four
hundred gallons (American) of dilute acid in water to the consistency
of cream, and spread over the surface of the acid and water with a ladle..

page_text: I allow it to stand for the night, and in the morning the liquid should
be the colour of light sherry wine.
Concentration. The charred stuff having thoroughly settled I syphon
off the liquid with great care into the evaporating pans and boil it down
as fast as possible; it does not require much care until it is over 54
degrees Beaume, and then if it has not been properly cleared it may
foam a little; should this prove to be the case I concentrate the same
to 60 degrees Beaume again and repeat the alumina process, for if it
shows signs of foaming at 54 degrees Beaume in the pans it is sure to
foam in the still. When concentrated to the required strength in the
pans to 58 degrees or 60 degrees Beaume I allow the same to cool to
about 200 degrees Fahrenheit, and then run it into the still.
•
Distillation. In distilling I heat gently at first with man-hole open,
when the acid fumes are coming off pretty freely I close the man-hole
and drive vapour through the gooseneck, testing the acid from time to
time, and when 66 degrees Beaume (hot) has been reached draw the fire
and allow the same to cool. The acid is then ready for the refiner when
allowed to cool sufficiently to draw off into carboys.
.
Statement of works required for 60 carboys (of spent acid) per day,
namely, two separators or square tanks of about one thousand
(American) gallons, capacity cach, say, five feet long, five feet wide, and
five feet deep, made of two-inch plank, and lined with lead (eight
pounds to the square foot), one dry lead coil, one inch diameter, and one
hundred feet long at the bottom of each tank. The end of the coil is
conducted over the side of either tank with a steam cock to regulate the
discharge of the steam; then in each tank another coil of lead pipe of
same size (one inch) in diameter, but only about fifteen feet long, the
steam through these last pipes to be discharged directly into the tank,
but checked when signs of foaming are visible. The charring pan should
be four feet wide, six feet long, and four feet deep, resting on an iron
plate balf inch thick to cover the top of the furnace, the lead of which
this pan is made should be about fourteen pounds to the square foot,
brickwork to extend up the sides of the pan for, say, one foot, then two-
inch plank to the top to keep the pan in shape (this pan should be
cleaned well after each batch, because anything remaining on the
bottom would soon eat a hole through the lead). The iron plate should
be four inches larger each way than the charring pan, so as to allow the.
brickwork to rest on it, and should be supported in the centre with a

page_text: cross bar of cast iron. Alumina pans or more properly vats, two in
number, should be made of two-inch plank lined with light lead, say,
three pounds to the square foot, they should be six feet square on the
top, two feet square on the bottom, and six feet deep. I syphon off the
clear dilute acid into the evaporating pans with great care, the liquid
should be the colour of light sherry wine. The evaporating pans, which
are three in number, should be made of lead (eight pounds to the
square foot), say, four feet wide, six feet long, and fifteen inches deep,
resting on cast-iron plates half-inch thick, supported the same way as
the charring pan.
The brickwork to run halfway up the sides, and to be
planked to the top to keep the same in shape. There should be a
separate furnace under cach pan with no connection with each other.
The still to be of white cast iron five and a half feet wide on the belly,
and four and a half feet deep, the cover to be of same metal, and to be
of the same shape as the bottom of the still, so that when the cover is on
the whole still will resenible an egg in shape. I use asbestos for packing,
and fasten the cover to the still by means of, say, fifteen three-quarter-
inch iron bolts. The still is of course heated by a furnace, and must be
built solidly in brickwork; the brickwork should come well over the
cover, and so as not to allow the cold air to strike a larger surface than
possible. The manhole is to be placed in front of the still cover to work
on a pivot, but to fit tight when required. The gooseneck may be on
the back if convenient, and should be about eight inches diameter at the
junction with the still cover tapering down to about three inches. It
need not be over two and a half feet long, and must also be of white
metal. To the gooseneck I attach about fifteen feet of one-and-a-half
inch lead pipe coil, say, ten feet of it, in a barrel to be continually filled
with cold water from a hydrant, the end of the pipe, to remain open so as
to allow the vapour to escape, the end should be brought out of the
barrel near the bottom, the vapour escaping into a larg vessel filled
with water. The furnaces under the still, evaporating pans, and charring
pans, are built in the usual way, a good draft being the most important
feature. Fifteen pounds of steam from a boiler sufficiently large to
drive a twenty-horse power engine conveyed through inch piping will be
all that is necessary for the purpose of separation. There should be a
small groove or trench on the inside of the cover of the still around the
base or place where it connects with the still and encircling the whole
cover opening into the bottom or lower side of the gooseneck. When
the water evaporates it collects in drops on the inside of top of the still

page_text: and runs down the side, and being caught in the groove or trench is run
off and prevented from falling back into the still.
The Drawings accompanying this Specification which illustrates the
details of the apparatus herein referred to, will be understood from the
figures and descriptive notes placed on the same sheet with them.
Having now particularly described and ascertained the nature of my
said Invention, and in what manner the same is to be performed, I
hereby declare that I claim the Invention of the process for the recovery,
purification, and revivification of sulphuric acid spent and deteriorated
as aforesaid, a principal feature whereof is the recovery, purification, and
revivification by means of oxygen gas in the nascent state of the spent
and deteriorated sulphuric acid.
In witness whereof, I, the said George Willoughby Hemans, have
hereunto set my hand and seal, this Eleventh day of November,
in the year of our Lord One thousand eight hundred and seventy.
G. WILLOUGHBY HEMANS. (L.S.)
Witness,
R. MARSDEN LATHAM,
21, Cockspur Street,
Charing Cross,
London.

page_text: 1. Separator (There are two separators
which are placed side by side
B. Charring Pan.
C. Alumina Vat (There are two alumina
vats which are placed side by side.
D.D.D.Evaporating pans.