IMPROVEMENTS IN THE TREATMENT OF MIXTURES OF SULPHURETTED HYDROGEN AND OTHER GASES TO OBTAIN THE SULPHUR OF THEIR SULPHURETTED HYDROGEN AS SULPHUROUS ACID
Year: 1883

page_text: LETTERS PATENT to Carl Friedrich Claus, of Mark Lane, in the City of
London, Chemist for an Invention of "IMPROVEMENTS IN THE TREATMENT
OF MIXTURES OF SULPHURETTED HYDROGEN AND OTHER GASES TO OBTAIN
THE SULPHUR OF THEIR SULPHURETTED HYDROGEN AS SULPHUROUS ACID
"
London, Chemist for an Invention of "IMPROVEMENTS IN THE TREATMENT
OF MIXTURES OF SULPHURETTED HYDROGEN AND OTHER GASES TO OBTAIN
THE SULPHUR OF THEIR SULPHURETTED HYDROGEN AS SULPHUROUS ACID
"
PROVISIONAL SPECIFICATION left by the said Carl Friedrich Claus at
the Office of the Commissioners of Patents on the 31st December 1883.
16
CARL FRIEDRICH CLAUS, of Mark Lane, in the City of London, Chemist,
IMPROVEMENTS IN THE TREATMENT OF MIXTURES OF SULPHURETTED HYDROGEN
AND OTHER GASES TO OBTAIN THE SULPHUR OF THEIR SULPHURETTED HYDROGEN
AS SULPHUROUS ACID."
This invention consists in a method of burning into sulphurous acid gas and
vapor of water the sulphuretted hydrogen contained in mixtures of sulphuretted
hydrogen and other gases, and especially the sulphuretted hydrogen contained in
such mixtures of gases as are obtained by treating what is known as alkuli
waste" (being the residue of the manufacture of soda by the Leblanc process) by
products of combustion or by the gases from lime-kilns.
"
To burn the said sulphuretted hydrogen into sulphurous acid gas and vapor of
water, if the said mixture of gases containing such sulphuretted hydrogen has not
already associated with it the required proportion of free oxygen, I add thereto
so much atmospheric air that the total quantity of free oxygen in the resulting
mixture of gases shall be at least the quantity necessary for the reaction:
=
HS+30 HO + SO₂,
and I then pass the mixture of gases now thus containing not less than enough
oxygen to burn both the hydrogen and the sulphur of the sulphuretted hydrogen
contained therein through a bed or layer of powder or fragments or small pieces
of solid material maintained at a suitable temperature, as will hereinafter be
explained.
The said bed or layer of powder or fragments or small pieces of solid material
must be contained in a box or kiln which must be completely closed, except that

page_text: it must communicate with a pipe or pipes by means of which the mixture of gases
containing sulphuretted hydrogen and free oxygon may be fed into it, and also
with a pipe or pipes for conveying the mixture of sulphurous acid gas and other
gases which pass off from the top of the said bed to the apparatus in which the
sulphurous acid is to be utilized. The said kiln, though I do not confine myself,
to such form of it, may conveniently be an iron box, lined with brick, or fireclay,
or a mere brick chamber, not clothed externally with iron, and may conveniently
be furnished with a false bottom pierced with holes, or with a grid or other
equivalent appliance, upon which the bed or layer of powder or fragments or
pieces of solid material should be spread, and the mixture of gases containing
sulphuretted hydrogen and enough oxygen to burn that sulphuretted hydrogen
into sulphurous acid and vapour of water may be fed into the kiln either below
such bed or above it, the mixture of gases and vapors resulting from the reactions
which take place in the interstices of the material of which the bed contained in
the kiln is composed passing out of the kiln in the opposite direction.
The bed or layer of powder, fragments, or pieces of solid material contained in
the said kiln may consist of almost any not readily fusible solid substance. The
more porous the material of which that bed is formed the better, and the smaller
the fragments of which it is composed also the better, provided only that such
fragments be not too small to permit of the mixture of gases passing sufficiently
freely through the bed or layer of them. In my experimental operations I have
obtained good results when using the said material in powder, and also when
employing it in fragments or lumps of very various sizes. The depth of bed which
I have employed has varied from a few inches to several feet, and in practice it
may vary according to the state of division of the material of which the bed is
composed, and also according to the rate at which the mixture of gases is fed into
the kiln. Except in the case to be mentioned below, the bed must always be
heated up, by any convenient means, before the mixture of gases is first admitted
into the kiln; but the heat of the reactions taking place in the interstices between
the fragments or small pieces of which the said bed is composed will afterwards
maintain its temperature sufficiently, if the operation be conducted continuously,
if the mixture of gases upon which it is performed be sufficiently rich in
sulphuretted hydrogen and free oxygen, and if the rate at which that mixture
of gases is fed into the kiln be not too slow. In other cases it will be necessary
to supplement the heat of the reaction in question by heat from some other source
applied to the bed or layer of pieces fragments or powder of solid material
externally or otherwise as may be most convenient in each case.
Among the almost innumerable substances, of any one of which, or of a mixture
of any two or more of which, the bed in question may be formed, I would indicate,
as perhaps the cheapest and most convenient (though I do not confine myself to
these substances) fragments of brick, oxide of iron, oxide of manganese, asbestos
(coated or impregnated or not with a metal, an oxide, or a salt) alumina, oxide of
zinc, carbonate of zinc, lime, and calcium carbonate,
When the bed contained in the aforesaid kiln is composed either wholly or in
part of hydrated oxide of iron, hydrated oxide of manganese, or analogous
substance, it need not be heated up before commencing to pass into the kiln
the mixture of gases containing sulphuretted hydrogen and free oxygen. Such
hydrated oxides can start the required reaction or reactions at ordinary
temperatures, and though the heat developed by that reaction or those reactions
soon renders the said hydrated oxides anhydrous or nearly so, it at the same
time heats the bed which at first consisted wholly or in part of such hydrated
oxide or oxides to such temperature that, if the conditions otherwise be as above
indicated, it can henceforth maintain such reaction or reactions, notwithstanding
that the said oxide or oxides have become nearly or completely dehydrated.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Carl Friedrich Claus in the Patent Office on the 30th June
1884.
CARL FRIEDRICH CLAUS, of Mark Lane, in the City of London, Chemist,
"IMPROVEMENTS IN THE TREATMENT OF MIXTURES OF SULPHURETTED HYDROGEN
AND OTHER GASES TO OBTAIN THE SULPHUR OF THEIR SULPHURETTED HYDROGEN
AS SULPHUROUS ACID
"
This Invention consists in a method of burning into sulphurous acid gas and
vapour of water the sulphuretted hydrogen contained in mixtures of sulphuretted
hydrogen and other gases and especially the sulphuretted hydrogen contained in
such mixtures of gases as are obtained by treating what is known as
waste" (being the residue of the manufacture of soda by the Leblanc process) by
products of combustion or by the gases from lime-kilns.
" alkali
To burn the said sulphuretted hydrogen into sulphurous acid gas and vapour
of water, if the said mixture of gases containing such sulphurette hydrogen has
not already associated with it the required proportion of free oxygen, I add
thereto so much atmospheric air that the total quantity of free oxygen in the
resulting mixture of gases shall be at least the quantity necessary for the
reaction:-
HS+30=H₂O + SO₂,
and I then pass the mixture of gases, now thus containing not less than enough
oxygen to burn both the hydr gen and the suphur of the sulphuretted bydrogen
contained therein, through a bed or layer of powder or fragments or small pieces
of solid material maintained at a suitable temperature, as will hereinafter be
explained.
The aid bed or layer of powder or fragments or small pieces of solid material
must be contained in a box or kiln which must be completely closed, except that
it must communicate with a pipe or pipes by means of which the mixture of gases
containing sulphuretted hydrogen and free oxygen may be fed into it, and also
with a pipe or pipes for conveying the mixture of sulphurous acid gns and other
gases which pass off from the top of the said bed to the apparatus in which the
sulphurous acid is to be utilized. The said kiln, though I do not confine myself
to such form of it, may conveniently be an iron box, lined with brick, or fireclay,
or a mere brick chamber, not clothed externally with iron, and may conveniently
be furnished with a false bottom pierced with holes, or with a grid or other
equivalent appliance, upon which the bed or layer of powder, fragments or pieces
of solid material should be spread, and the mixture of gases containing sulphuretted
hydrogen and enough oxygen to burn that sulphuretted hydrogen into sulphurous
acid and vapour of water may be fed into the kiln either below such bed or above
it, the mixture of gases and vapours resulting from the reaction which takes place
in the interstices of the material of which the bed contained in the kiln is
composed passing out of the kiln in the opposite direction.
The bed or layer of powder, fragments or pieces of solid material contained in
the said kiln may. consist of almost any not readily fusible s did substance. The
more porous the material of which that bed is formed the better, and the smaller
the fragments of which it is composed also the better, provided only that such
fragments be not too small to permit of the mixture of gases passing sufficiently
freely through the bed or layer of them. In my experimental operations, I have
obtained good results when using the said material in powder and also when
employing it in fragments or lumps of very various sizes; the depth of bed which
I have employed has varied from a few inches to several feet and in practice it
may vary according to the state of division of the material of which the bed is

page_text: compose, and also according to the rate at which the mixture of gases is fed
into the kiln. Except in the case to he mentioned below, the bed must always be
heated up by any convenient means, before the mixture of gases is first admitted
int the kiln; but the heat of the reactions taking place in the inter-tices between
the fragments or small pieces of which the said bed is composed will afterwards
maintain its temperature sufficiently, if the operation be conducted continuously, if
the mixture of gases upon which it is performed be sufficiently rich in sulphuretted
hydrogen and free oxygen, and if the rate at which that mixture of gases is fed
into the kiln be not too slow. In other cases it will be necessary to supplement
the heat of the reaction in question by heat from some other source applied to the
bed or layer of pieces, fraginents or powder of solid material externally or
otherwise as may be most convenient in each case, or by heating the air, or the
gases containing the sulphuretted hydrogen, or both, or by admitting combustible
gas such as carbonic oxide together with the sulphuretted hydrogen and air.
Among the almost innumerable substances, of any one of which, or of a
mix ure of any two or more of which, the bed in question may be formed, I would
indicate, as perhaps the cheapest and most convenient, (though I do not confine
myself to these substances) fragments of brick, oxide of iron, oxide of manganese,
asbestos, (coated or impregnated or not with a metal, an oxide, or a salt) alumina,
oxide of zinc, carbonate of zine, lime, and calcium carbonate.
When the bed contained in the aforesaid kiln is composed either wholly or
in part of hydrated oxide of iron, hydrated oxide of manganese or analogous
substance, it need not be heated up before commencing to pass into the kiln the
mixture of gases containing sulphuretted hydrogen and free oxygen. Such hydrated
oxides can start the required reaction or reactions at ordinary temperatures and,
though the heat developed by that reaction or those re-actions soon renders the said
hydrated oxides anhydrous or nearly so, it at the same time heats the bed which at
first consisted wholly or in part of such hydrated oxide or oxides to such temperature
that, if the conditions otherwise be as above indicated, it can henceforth maintain
such reaction or reactions, notwithstanding that the said oxide or oxides have
become nearly or completely dehydrated.
Having thus fully described my said invention and the manner of performing
the same I wish it understood that what I claim as the invention to be secured
to me by the herein before in part recited Letters Patent consists in effecting the
combustion into sulphurous acid gas and vapour of water, of the sulphuretted
hydrogen contained in a mixture of sulphuretted hydrogen and other gases by
adding to such mixture of gases, if sufficient free oxygen be not contained
therewith already, a quantity of air containing enough or more than enough
oxygen to burn both the hydrogen and the sulphur of the said sulphuretted
hydrogen, and then passing a mixture of sulphuretted hydrogen and other gases
containing such quantity of air through a bed or layer of fragments of suitable
solid material, substantially as is above described, the said bed or layer of
fragments of solid material being maintained at a suitable temperature either by
the heat of the reaction which takes place as the mixture of gases passes through
the said bed or layer of fragments of solid material, or by heat from any other
source applied thereto in any convenient way.
In witness whereof I the said Carl Friedrich Claus have hereunto set my
hand and seal this Twenty eighth day of June in the year of our Lord One
thousand eight hundred and eighty four.