Improvements in the Treatment of Gases and Recovering of Sulphur from Sulphuretted Hydrogen Evolved in Various Manufacturing Processes.
Year: 1888

page_text: Date of Application, 1st Dec., 1888
Complete Specification Left. 26th Aug., 1889-Accepted, 30th Nov., 1889
PROVISIONAL SPECIFICATION.
Improvements in the Treatment of Gases and Recovering of
Sulphur from Sulphuretted Hydrogen Evolved in Various
Manufacturing Processes.
I JOHN BARROW, of the Dalton Chemical Works, Clayton near Manchester, in
the County of Lancaster, Manufacturing Chemist, do hereby declare the nature of
this invention to be as follows:-
As is well known, sulphuretted hydrogen alone or with other gases is evolved in various
manufacturing operations including for example such as are hereinafter enumerated,
and is a product giving rise to much trouble in consequence of requiring special
treatment to obviate public nuisance. It is largely produced from the sulphides of
alkaline earths and sulphides of the alkalies when these bodies are treated with
carbonic acid, or mineral acids; also in the distillation of coal for the production of
gas or oil; also in the manufacture of bisulphide of carbon; also in the distillation
of ammonia water for the production of salts of ammonia.
Many methods of treatment have been adopted or proposed, but I have discovered
that the sulphuretted hydrogen can be rendered practically inoffensive and sulphur be
recovered in an almost pure condition by my present invention, according to which
the sulphuretted hydrogen whether alone or mixed with other gases is caused to pass
through, or to meet, or to come into contact in any convenient manner with a solution
of perchloride of iron or perchloride of manganese and this treatment is continued
until precipitation of sulphur has ceased. I find that the chloride of manganese and
the chloride of iron after reduction from the condition of perchlorides by sulphuretted
hydrogen are very easily changed to the condition of perchloride in readiness for
re-use by bringing the chloride in solution into contact with the higher oxides of iron
or manganese and by this treatment I am enabled to re-use them an indefinite
number of times. The solution reduced completely or partially from the state of
perchloride is left to deposit sulphur or it may have the sulphur filtered from it, and
when the sulphur is removed the liquors are caused to pass through beds of the
higher oxides of iron or manganese to restore them to their previous condition of
perchlorides for re-use as above indicated.
The gases associated with the sulphuretted hydrogen as for examples carbonic acid,
ammonia, bisulphide of carbon, may be utilized after separation of the sulphuretted
hydrogen from them, instead of being wasted as they at present are in some of the
hereinabove indicated manufacturing operations. In particular carbonic acid gas
arising during the manufacture of sulphate of ammonia may after the separation of
the sulphuretted hydrogen by the use of the perchlorides as above described be applied
to the purpose of liberating further quantities of sulphuretted hydrogen from the
sulphides of the alkalies or sulphides of the alkaline earths.
Dated thin 1
1000
W. LLOYD WISE,
Per F. J. Brougham,
46, Lincoln's Inn Fields, London, W.C., Agent for the Applicant.

page_text: COMPLETE SPECIFICATION.
in
Improvements in the Treatment of Gases and Recovering of
Sulphur from Sulphuretted Hydrogen Evolved Various
Manufacturing Processes.
I, JOHN BARROW, of the Dalton Chemical Works, Clayton, near Manchester, in
the County of Lancaster, Manufacturing Chemist, do hereby declare the nature of
this invention and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement:-
As is well known, sulphuretted hydrogen alone or with other gases is evolved in
various manufacturing operations including for example such as are hereinafter
enumerated, and is a product giving rise to much trouble in consequence of requiring
special treatment to obviate public nuisance. It is largely produced from the
sulphides of alkaline earths and sulphides of the alkalies when these bodies are treated
with carbonic acid, or mineral acids; also in the distillation of coal for the production
of gas or oil; also in the manufacture of bisulphide of carbon; also in the distillation
of ammonia water for the production of salts of ammonia.
Many methods of treatment have been adopted or proposed but I have discovered
that the sulphuretted hydrogen can be rendered practically inoffensive and sulphur be
recovered in an almost pure condition by my present invention, according to which
the sulphuretted hydrogen whether alone or mixed with other gases is caused to pass
through, or to meet, or to come into contact in any convenient manner with a solution
of perchloride of iron or perchloride of manganese and this treatment is continued
until precipitation of sulphur has ceased. I find that the chloride of manganese and
the chloride of iron after reduction from the condition of perchlorides by sulphuretted
hydrogen are very easily changed to the condition of perchloride in readiness for
re-use by bringing the chloride in solution into contact with the higher oxides of iron
or manganese and by this treatment I am enabled to re-use them an indefinite number
of times. The solution reduced completely or partially from the state of perchloride,
is left to deposit sulphur, or it may have the sulphur filtered from it, and when the
sulphur is removed the liquors are caused to pass through beds of the higher oxides
of iron or manganese to restore them to their previous condition of perchlorides for
re-use as above indicated.
The gases associated with the sulphuretted hydrogen, as for examples carbonic acid,
ammonia, bisulphide of carbon, may be utilized after separation of the sulphuretted
hydrogen from them, instead of being wasted as they at present are in some of the
hereinabove indicated manufacturing operations. In particular carbonic acid gas
arising during the manufacture of sulphate of ammonia may after the separation of
the sulphuretted hydrogen by the use of the perchlorides as above described, be
applied to the purpose of liberating further quantities of sulphuretted hydrogen from
the sulphides of the alkalies or sulphides of the alkaline earths.
In order that my invention may be conveniently carried into practice I so arrange
the several parts of my apparatus, that each operation shall follow in succession with
as little manual labour as possible, and as shewn in the drawings annexed in
which,
Fig. 1 is a vertical section; and
Fig. 2 a plan of the apparatus.
Fig. 3 is a vertical section through the settlers, filter and revivifiers on the line x c
Fig. 2.
Fig. 4 is a longitudinal vertical section through the revivifiers, a vessel for
containing a solution of perchloride, and a filter, part of the latter being shewn in
elevation.
A is a washer and B a scrubber as commonly used in gas works. F¹ to F" are
settling tanks. A is a pipe by which solution can pass from the washer into a pipe F'
that is provided with a number of branch pipes F each arranged to communicate
with one of the settlers as shown and provided with a valve F" for controlling the

page_text: communication. Each of the settlers is provided with an outlet pipe with valve F10
by which it can be placed in communication with one of two pipes G* connected to
an outlet pipe G¹. The settlers F¹ to F are also in communication with each other
by holes F (Figs. 2 and 3) in the walls between adjacent settling chambers. By
this construction liquor can be caused to pass through the successive chambers as well
as from chamber F to chamber F¹ thus there may be one or there may be two or
more of the settlers working in succession as may be desired. G is a filter arranged
below the outlet pipes G₁ of the settling tanks, and above a revivifier H. C is a vessel
for containing solution of a perchloride. This vessel C communicates by a pipe C"
with the revivifiers, and by a pipe C2 with a feeding tank C³ above the scrubber. The
gas to be treated passes through the washer and scrubber in the usual way, meeting or
being brought into contact in its passage with the solution of perchloride of iron or of
manganese flowing through these vessels, and in this way effecting the decomposition
of the sulphuretted hydrogen present in the gas. The washer and scrubber Bare
however supplemental to the usual washers and scrubbers for removing all tar and
ammonia from the gas. The course followed by other gases charged with sulphuretted
hydrogen will be the same, namely, through a washer and a scrubber the arrangement
of which can be varied to suit the requirements of various manufactories.
The course followed by the solution and the manner of treating it, may be thus
described. The solution of the perchloride in the vessel C is forced to the top of the
scrubber through which it is then caused to descend and fall into the washer through
the pipes D and E after becoming charged with sulphur. The resulting solution of
proto-chlorides of iron or manganese, or both, mixed with some perchloride of iron
and with sulphur, is caused to pass through a system of settlers F¹ to Fe for the
further purpose of allowing the sulphur to deposit. When found necessary by the
accumulation of sulphur, the liquid contents of the settling tanks are
run off
successively on to the filter bed G, when the sulphur will be left drained, ready for
removal and drying by any of the well known means; or it may be fused and
crystallized.
The liquors which pass through the filter bed G flow into the revivifier H which
comprises a vessel with a series of compartments the first two or more of which are
charged with burnt oxide or the higher oxides of iron, or with one of the higher
oxides of manganese, which revivify or reconvert the proto-chloride of iron or manganese
into perchloride of iron or manganese thereby making it suitable for again reducing
sulphuretted hydrogen. This operation may be assisted by heated air, or by a mixture
of steam and heated air. For this purpose air may be forced through pipes (super-
heaters) heated by a furnace and then through the oxides in the revivifier. The other
compartments of the vessel H are used as settlers for any oxide that may be washed
over with the regenerated perchloride. The perchloride then flows into the vessel C
and thus completes the cycle of operations.
As will be evident, the construction of the apparatus, the number of compartments
in the settler, the exact form of the filter bed and other details may be varied to suit
the requirements of different cases.
The description above given of the application to coal gas making, where the gas
must be of necessity utilized, will suffice to enable it to be understood how my
invention is to be used for treating other gases associated with sulphuretted hydrogen
in other manufacturing processes which may be collected and utilized in the same way,
as herein before mentioned.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The hereinabove described method or process of rendering sulphuretted hydrogen
practically inoffensive and recovering sulphur therefrom by subjecting the sulphuretted
hydrogen (whether alone or mixed with other gases) to the action of a solution of
perchloride of iron or perchloride of manganese (or both).

page_text: 2. Subjecting sulphuretted hydrogen (whether alone or mixed with other gases) to
the action of a solution of perchloride of iron or perchloride of manganese (or both)
for the purpose of recovering sulphur, and subsequently converting the proto-
chloride resulting from the reduction of the perchloride, to the condition of per-
chloride (in readiness for re-use) by contact with the higher oxides of iron or of
manganese.
3. The hereinabove described method or process of recovering sulphur from
sulphuretted hydrogen and utilizing the associated gases.
Dated this 26th day of August 1889.
W. Lloyd Wise,
JOHN BARROW.
46, Lincoln's Inn Fields, London, W.C., Agent for Applicant.