IMPROVEMENTS IN THE ECONOMICAL TREATMENT OF REFUSE OR WASTE ... MATTER CONTAINING SULPHUR."
Year: 1859

page_text: LETTERS PATENT to Thomas Spencer, of No. 192, Euston Road, Euston
Square, London, Analytical and Consulting Chemist, for the Invention
of "IMPROVEMENTS IN THE ECONOMICAL TREATMENT OF REFUSE OR WASTE
... MATTER CONTAINING SULPHUR."
PROVISIONAL SPECIFICATION left by the said Thomas Spencer at the
Office of the Commissioners of Patents, with his Petition, on the
9th April 1859.
.I, THOMAS SPENCER, of No. 192; Euston Road, Euston Square, London,
Analytical and Consulting Chemist, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE ECONOMICAL TREATMENT OF REFUSE OR
WASTE MATTER CONTAINING SULPHUR," to be as follows:-
The object of these improvements is to extract. the sulphur contained in the
offensive and deleterious matter accruing from the manufacture of alkaline
substances, and commonly known as "alkali waste," and also to extract the
sulphur contained in the spent lime used in the manufacture of gas.
First, the substance I prefer to employ for this purpose, in the first place, is
oxide of iron when combined with carbon, being that substance termed by me
"ferroso-ferric.carbide, or indifferently, carbide of the magnetic oxide of iron,.
for the first production of which, with several of its useful applications, a
Patent was obtained by me bearing the date of, June the 23rd, 1858, "&
numbered 1415,” in which its manufacture is fully described.
-Second, to extract the sulphur contained in the said waste matters, I also

page_text: employ in like manner the substance known as magnetic oxide of iron, at the
same time I prefer that which has been prepared by artificial means to that
found in the natural state. This oxide, as well as the above-named "magnetic
carbide," may be prepared from any of the ores of iron by means of heat along
with carbon, the details of which mode of procedure will be farther given in
my Final Specification.
.
Third, to extract the sulphur contained in the said waste matters, I also
employ in like manner the substance known to mineralogists as the "spathose
ore," which in itself consists of the carbonate of the protoxide of iron.
Fourth, to extract the sulphur contained in the said waste matters, I also
employ in like manner oxides. of manganese obtained from any of its ores.
I give. a preference, however, to the artificially prepared sesqui-oxide of this
metal; the details of tlie mode of procedure necessary for its preparation will
also be given in my Final Specification.
Fifth, to extract the sulphur contained in the said waste matters, I employ
in like manner the anhydrous peroxide of iron, or the bydrous peroxide,
though I prefer it after the water has been driven off by heat.
I may add, that ferruginous or manganic oxides obtained in any manner
are applicable to the purpose of this Invention; for example, the residual
ferruginous oxide obtained after the calcination of pyritic ores, or the manganic
refuse oxide accruing from the manufacture of chloride of lime, are available.
Were the substances I have enumerated obtained with equal convenience
and cost, I should prefer to use them in the order they are here placed, that
is to say, I prefer to use the combination of oxide of iron with carbon in the
first, and the prepared magnetic oxide in the second place, and so on as
regards the others.
To effect the separation of the sulphur from the aforesaid waste matters by
means of the above ferruginous or manganic agency, I first cause the said
sulphur to be disengaged in the state of sulphuretted hydrogen by means of
muriatic acid; giving the preference to this acid when it can be obtained
cheaply. If otherwise, I then use carbonic acid gas, produced by the
combustion of coal, coke, or charcoal, or any other carbonaceous material, or
from the calcination of lime. The sulphuretted hydrogen when obtained
from the alkali or other waste by the means here indicated, is made to pass
over or through layers of any of the substances above enumerated, and by
which means I obtain a mixture of sulphur and the carbonaceous or other
oxide employed for the reduction of the sulphuretted hydrogen. From the
mixture thus obtained, the sulphur is thon separated by distillation, or it may
be burned off in any suitable furnace, and thus produce sulphurous acid for

page_text: the manufacture of sulphuric acid. After the sulphur is liberated, the residual
carbonaceous or other oxide may again be used any number of times in
effecting the same object.
SPECIFICATION filed in pursuance of the conditions of the Letters Patent,
and of an Order of the Lord Chancellor, by the said Thomas Spencer
in the Great Seal Patent Office on the 15th October 1859..
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, THOMAS
SPENCER, of 192, Euston Road, Euston Square, London, Analytical and
Consulting Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Ninth day of April, in the year of our Lord
One thousand eight hundred and fifty-nine, in the twenty-third year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Thomas Spencer, Her special licence that I, the said Thomas Spencer,
my executors, administrators, and assigns, or such others as I, the said
Thomas Spencer, 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 ECONOMICAL TREATMENT OF REFUSE OR WASTE MATTER CONTAINING
SULPHUR," upon the condition (amongst others) that I, the said Thomas
Spencer, 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 Offico within six calendar months next and immediately after
the date of the said Letters Patent.
NOW KNOW YE, that I, the said Thomas Spencer, do hereby declare
the nature of my 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:-
My said Invention of "Improvements in the Economical Treatment of
Refuse or Waste Matters containing Sulphur," applies, firstly, to the treat-
ment of such waste matter containing sulphur as is produced in the ordinary
manufacture of soda or potash from sulphate of soda or sulphate of potash,

page_text: and is technically known as "alkali wasto" or "tank refuse;" also to the
treatment of such waste matter containing sulphur, as is produced in the
ordinary process of purifying coal gas, by means of hydrate of lime, and which
is commonly known as "waste gas lime," the object of such treatment being
to obtain sulphur from such waste matters by liberating the same therefrom
in a gaseous state combined with hydrogen, and acting upon such gaseous
sulphur by certain oxides herein-after mentioned, so as to convert such gaseous
sulphur into solid sulphur, either in a free or uncombined state, or in such a
state of combination as admits of sulphur being easily liberated therefrom, and
applied to useful purposes.
My said Invention applies, secondly, to the extraction of sulphur from
certain liquors which result from the action of water upon the waste matters
herein-before mentioned.
It is well known that both the said waste matters contain compounds in
which sulphur is combined with calcium and lime, also that when such com-
pounds are treated with acids, such as hydrochloric acid or carbonic acid, an
extrication of gaseous sulphur combined with hydrogen is effected, and that by
such treatment the greater part of the sulphur previously existing in such
waste matters is extricated therefrom in the state of sulphuretted hydrogen
gas.
•
In effecting one portion of my said improvements I cause sulphur previously
existing in such waste, matters, to be liberated therefrom in the state of
sulphuretted hydrogen gas by the action thereon of hydrochloric acid or
carbonic acid, and cause the gas so liberated to be conducted into contact
with certain oxides of iron, or of manganese (herein-after specified), by
which contact such sulphuretted hydrogen gas becomes decomposed, and the
sulphur previously contained therein in a gaseous state becomes deposited in
a solid form, producing a compound from which such sulphur can either be
separated and obtained as pure sulphur by distillation in closed vessels, or cau
be burned off with atmospherical air, producing sulphurous acid gas, which is
applicable to the various uses for which sulphurous acid gas obtained from
solid sulphur is ordinarily employed.
The oxides of iron which I prefer to employ for effecting the abstraction of
sulphur from such sulphuretted hydrogen gas (obtained from the waste
matters herein-before mentioned), are all such oxides of iron as contain a less
proportion of oxygen than is contained in peroxide of iron; also a certain
compound which I have designated as carbide of the magnetic oxide of iron,
for the preparation of which I have given full directions in the Specification of
a Patent which was granted to me on or about the Twenty-third day of June,

page_text: One thousand eight hundred and fifty-eight, for "Improvements in the Treat-
ment of Iron Ores and Ferruginous Sands, and certain Applications arising
therefrom."
Of the oxides of iron well suited for effecting the objects of my said
Invention, I may enumerate the native magnetic oxide of iron, the spathon
ore of mineralogists, bog iron ore, and the iron ore called hamatite; (par-
ticularly after these ores have undergone a preparation by roasting in closed
vessels), the oxide of iron obtained by burning off sulphur by means of atmo
spherical air from iron pyrites, and the oxide of iron which remains after
burning off sulphur by means of atmospherical air from the compound obtained
by the action of sulphuretted hydrogen gas on oxide of iron. Though I prefer
these oxides, those of other ferruginous ores are also applicable.
In reference to the different ferruginous bodies which are available for the
purpose of effecting the objects of my said Invention, I may state as the result
of my present experience, that those which contain the most considerable
proportions of protoxide or magnetic oxide are found to be the most energetic
in their action upon sulphuretted hydrogen, particularly when this action is
accomplished at moderate temperatures. As regards the use of hæmatite or
other peroxide of iron for such purpose, I may remark, that amongst a number
of samples of these oxides which I have examined, I have scarcely met with
any that was not affected by the magnet, and therefore indicating the presenco.
of a lower oxide. To the circumstance of this property being only slight in
this class of ferruginous oxides, I attribute their sluggish action upon
sulphuretted hydrogen at ordinary temperatures. When therefore from other
circumstances it may be found convenient to use hæmatite ores or oxides of
this character, including such oxide as is produced by calcining iron pyrites
with common salt, I prefer to subject them to a previous heating in closed
vessels either alone or preferably in mixture with carbonaceous matter, by
which treatment magnetic oxide of iron is developed; directions for which
will be found in the Specification of my Patent for the purification of gas
illuminating, bearing the date of December the Twenty-ninth, One thousand
cight hundred and fifty-seven.
Though it is obviously more convenient in practice to effect the decomposition
of sulphuretted hydrogen without any application of external heat, yet when
I am obliged to use sluggish ores which have not been calcined to accelerate
their action, I cause sulphuretted hydrogen to be brought into contact with
them, whilst they are heated to a temperature exceeding that of boiling water.
Under such circumstances I find that they extract the sulphur with more
ranidity

page_text: As my said Invention will be particularly applicable in connection with the
manufacture of soda, in which manufacture there is frequently much oxide of
iron produced as a result of the extraction of sulphur from pyritos, this oxide
is well suited for effecting the objects of my said Invention, both as regards con-
venience and economy. The oxides of manganese which I employ for
effecting the objects of my said Invention I may enumerate, are the native
black oxide or peroxide of maganese, and the native brown oxide or sesqui-
oxide of manganese, the various oxides of manganese obtained artificially;
also the oxide of manganese which remains after burning off sulphur by means
of atmospherical air from the compound obtained by the action of sulphuretted
hydrogen gas on oxide of manganese. When I use peroxide of manganeso
I prefer to subject this to a preparatory treatment by heating it in a closed
vessel in mixture with carbonaceous matter, as hercin-before described, in
reference to the treatment of peroxide of iron, in my Patent of December
the 29th, 1857.
I have berein-before stated that in order to effect one portion of the objects
of my said Invention, I cause sulphur in the state of sulphuretted hydrogen
gas to be extricated from the waste matters herein-before mentioned, and to be
conducted into contact with oxides of iron or manganese, and that by such
contact such sulphuretted hydrogen becomes decomposed, and sulphur pre-
viously contained therein in a gaseous state becomes deposited in a solid form.
By the reaction which occasions such decomposition, tho oxide employed
gradually loses its capability of effecting the decomposition of sulphuretted
hydrogen, but such capability is restored by the contact of atmospherical air.
I therefore effect this portion of the objects of my said Invention either by
causing the oxide employed to be alternately placed in contact with sulphu-
retted hydrogen gas (obtained from the waste matters herein-before mentioned)
and with atmospherical air; or I cause atmospherical air to be mingled with
such sulphuretted hydrogen gas and the mixture of gases to be brought into
contact with the oxide employed.
"
I continue to use the same oxide for effecting the decomposition of such
sulphuretted hydrogen gas, until I find the decomposing action to become
sluggish in consequence of the accumulation of sulphur therein. I then
remove the compound produced, and if I desire to obtain free sulphur there-
from, I introduce it into a retort (preferably made of fire clay), and by the
application of beat, sulphur is distilled over, and I collect this by means of
suitable apparatus; or if I wish to apply such sulphur to the production of
sulphurous acid, 1 introduce the said compound containing sulphur into kilns,
or other suitable apparatus (such as are commonly used for burning off sulphur

page_text: from iron pyrites), and by the access of atmospherical air I cause such sulphur
to be burned, and thereby to produce sulphurous acid. In either case the
residuum remaining from the process of distillation or combustion contains
oxide of iron or oxide of manganese in a state very suitable for effecting the
decomposition of a further quantity of sulphuretted hydrogen.
In effecting that part of my said Invention which applies to the extraction
of sulphur from liquors obtained from the waste matters herein-before referred
to by the action of water thereon, I may state that such waste matters are
commonly disposed of by placing them in heaps in the open air, and that
such heaps being exposed to the dissolving action of water filtering through
the same, yield an offensive liquor which contains sulphur and lime in a state
of combination. It also occurs sometimes in the neighbourhood of soda
manufactories that such offensive liquors become mingled with hydrochloric
acid, which, combining with the lime contained in such liquors, causes the
liberation of sulphur in the state of sulphuretted hydrogen, and thereby the
offensiveness is greatly increased. I effect this part of my said Invention by
causing such offensive liquors (whether previously mingled with bydrochloric
acid or not) to filter through beds or layers of oxide of iron, preferring to use
such oxide as contains the largest proportionate quantity of magnetic oxide.
By such filtration, sulphur previously contained in such offensive liquors
becomes deposited in a solid form, and produces a compound with the oxide
of iron employed, from which sulphur may be extracted by distillation or com-
bustion with atmospherical air. I effect such filtration by the use of such
tanks or vessels as are commonly employed for the filtration of water for the
supply of towns, except that I construct such tanks or vessels in such manner
that I can run off the liquor therefrom, and expose the oxide of iron contained
therein to atmospheric air. I use two such tanks or vessels alternately, one
being employed for filtration of such liquors, whilst the contents of the other
are being exposed to atmospherical air. I place the oxide employed in such
tanks or vessels (in the form of lumps or of coarse powder), and I continue to
use the same portion of oxide until I find its purifying action to have become
sluggish by the accumulation of sulphur in mixture therewith. I then
remove the compound thus obtained and extract sulphur therefrom either by
distillation or combustion; the residuum of such distillation or combustion_
being suitable to be applied for the extraction of a further quantity of sulphur
from the offensive liquors obtained from the waste matters containing sulphur
herein-before mentioned.
In effecting the extrication of sulphur (in a gaseous state combined with
hydrogen) from the waste matters herein-before mentioned by manne

page_text: bydrochloric acid, I introduce such waste matters (with as little delay as
possible after these are withdrawn from the apparatus in which they have been
produced) into vessels constructed of Yorkshire flag-stones, or of timber
soaked in coal tar, and put together in such manner as to render them
imperious to liquids and gases. I provide a perforated shelf or false bottom
in each of such vessels, on which the waste matter is supported. I provide
also a pipe for conducting away from such vessel the gases which may be
generated therein by the action of hydrochloric acid ou such waste matters,
and another pipe for the introduction of hydrochloric acid into such vessel;
also an aperture at the lower part of such vessel for running off the liquid
chloride of calcium produced, and an aperture at the upper part of such vessel
for the introduction of the waste matter therein. Having charged such vessel
with the waste matter, I close up the aperture, and I introduce bydrochloric
acid. The action of such acid on the waste matter causes the evolution of
sulphuretted hydrogen gas, which passes off through the gas pipe, and 1
continue such introduction of hydrochloric acid until I judge the vessel is
nearly filled. I then run off the liquid chloride of calcium, and introduce a
fresh charge of waste matter and hydrochloric acid into such vessel.
In effecting the extrication of sulphur in a gaseous state combined with
hydrogen from the waste matter (herein-before mentioned as produced in the
manufacture of soda and potash) by means of carbonic acid gas, I prefer to
apply such gas to such waste matter in the apparatus in which the lixiviation
of the alkaline material has been effected. An apparatus by the use of which
this application can be conveniently effected is described in the Specification
of a Patent granted to William Gossage, bearing date on or about the Ninth
of November, 1852, for "Improvements in Obtaining Sulphur from certain
Metallic Sulphurets," such Specification also containing a description of
apparatus and method of working which I prefer to employ for the obtainment
of carbonic acid gas to be applied for the extrication of sulphuretted hydrogen
from the waste matters hercin-before mentioned, no claim being made in this
Patent for this form of apparatus.
Having obtained from the said waste matters sulphur in a gascous form
combined with hydrogen, constituting sulphuretted hydrogen gas,. I cause such
gas to be conducted into contact with some of the compounds of iron or of
which I have herein-before mentioned. For this purpose I prefer
manganese,
to employ an apparatus consisting of a series of chambers constructed of brick-
work, set in Roman cement, similar to the chambers which are commonly
employed for the manufacture of chloride of lime. I provide cach of these
chambers with a number of perforated shelves or floors extending the whole

page_text: width and length of the chambers, and about one foot distant from each other.
Upon these shelves I place the compound of iron or manganese which I employ,
preferring to use this in the state of lumps about the size of walnuts. I
arrange the connection of such chambers with each other, and also with the
pipe supplying sulphuretted hydrogen gas, in such manner that I can cause
such gas to be passed through each chamber consecutively; also in such
manner that I can cut off the connection of each chamber with the supply of
sulphuretted hydrogen gas, whilst I cause the contents of such chamber to be
exposed to a current of atmospherical air.
In place of using chambers for this purpose, I can employ a circular tower,
constructed of brickwork, making this about six feet diameter, and twenty
feet high. Having filled such tower with the compound of iron or manganese
which I employ, I connect the lower part of such tower with the supply pipe
of sulphuretted hydrogen gas, and cause the gas to percolate through the
contents of the tower; I add atmospheric air to the gas, or I make an
alternate application of it and of atmospheric air to the contents of the tower.
When I find the compound of iron or of manganese employed in such
chambers or tower to be sufficiently impregnated with sulphur, I remove such
compound and extract the sulphur therefrom by the means herein-before
mentioned.
In effecting the above purposes, I prefer to use the apparatus I have
herein described, though I by no means confine myself to it, as no doubt
further experience will suggest improvements thereon.
I claim as my Invention, as secured to me by the herein-before in part
recited Letters Patent, the use of the oxides, ores, and other compounds of
iron, and the oxides of manganese already referred to by me for the obtainment
of sulphur from the hitherto refuse or waste matters hercin-before mentioned
as containing sulphur.
In witness whereof, I, the said Thomas Spencer, have hereunto set my
hand and scal, this Eighth day of October, in the year of our Lord