Hydrogen.
Year: 1888

page_text: Hydrogen.
We EDWARD WILLIAM PARNELL and JAMES SIMPSON of 8 Rumford Place Liver-
pool in the County of Lancaster Manufacturing Chemists, do hereby declare the
nature of this invention to be as follows:-
When sulphuretted hydrogen is burned with a limited quantity of air in a chamber
lined with brick or other heat retaining material with the object of effecting the
reaction H. S+0= H₂O+S and the products of such combustion are cooled it has
been found that the sulphur produced is always far short of the theoretical quantity,
the loss being partly due to the escape in the gaseous form of a mixture of sulphuretted
hydrogen and sulphurous acid and partly to the formation of polythionic acids (mostly
tetrathionic) which to a considerable extent are found mixed with the wet sulphur
mud which is deposited in the cooling chambers. The formation of these thionic acids
we find to be caused by a reverse action between the sulphur originally formed and
the aqueous vapor. Also, when sulphuretted hydrogen and sulphurous acid are
brought into contact in the presence of water, combination takes place with formation
of sulphur and water, which reaction (provided the whole of the sulphur should be
found in the solid form) may be represented by the formula SO, +2 H, S = 2H,O+3S
but as in the other reaction above mentioned, the product of sulphur is in practice
found to fall far short of the theoretical quantity, while polythionic acids, mostly
tetrathionic are found in the liquid. The sulphur formed in this method of working
is not precipitated in the solid form to any considerable extent, but remains in a quasi
soluble condition: but if the acid formed in the liquid be neutralized by a suitable
base such as calcium sulphide, the sulphur will separate in the solid form. If the
thionic acids or thionates formed in this operation are subjected-after neutralization
to the action of heat and steam pressure, they will be decomposed with precipitation
of sulphur and evolution of sulphurous acid.
The object of our invention is by combining the operation of the first reaction above
mentioned by the bot process in a special manner with the operation of the second

page_text: reaction by the liquid process, together with a special treatment of the thionic acids
formed to get a much larger yield of sulphur from a given quantity of sulphuretted
hydrogen than has hitherto been obtained by operating either of these processes
separately.
In carrying our invention into practice we burn the sulphuretted hydrogen and air
in any convenient way in a combustion chamber lined with brick or clay, and conduct
the hot gases through a chamber filled loosely with brick or other heat retaining
material to a cooling chamber or series of cooling chambers where sulphur will be
deposited together with some polythionic acids as before mentioned. This method of
producing sulphur from sulphuretted hydrogen is well known having been described
in a Provisional specification filed 15 Feb. 1883 No. 844 by Philip John Worsley.
In adjusting the supply of sulphuretted hydrogen and air to the combustion chamber
we keep the sulphuretted hydrogen in excess, as we find that by so doing the formation
of the polythionic acids is considerably reduced. The gas escaping from the cooling
chamber containing an excess of sulphuretted hydrogen we bring in contact with
water containing sulphurous acid in a scrubber or other convenient apparatus, when
sulphur will be formed together with a certain amount of polythionic acids, produced
in this reaction or already existing in the gases from the combustion chamber. We
agitate the wet sulphur mud containing polythionic acids which were deposited in the
cooling chambers in the first operation, as also any precipitate from the second
operation with calcium, polysulphide solution or waste drainage or other suitable
alkaline sulphide or base, when the polythionic acids will be neutralized (with evolution
of sulphuretted hydrogen when a sulphide is used for neutralizing) and we treat the
mixture thus produced with heat and steam pressure in a sulphur melter or other
similar vessel in the ordinary way in which sulphur is melted. By this operation the
polythionic acids are decomposed yielding sulphur sulphurous acid and sulphuretted
hydrogen. The sulphuretted hydrogen evolved in the before mentioned neutralization
of the polythionic acids as also any sulphurous acid and sulphuretted hydrogen pro-
duced by the decomposition of the polythionic acids in the sulphur melter we convey
back to any suitable part of the plant where it can be utilized. The saline solution
resulting from the neutralization of the polythionic acids is used repeatedly for bringing
the sulphuretted hydrogen and sulphurous acid in contact as herein before mentioned.
The loss incurred by the removal from time to time of some liquor with the pre-
cipitated sulphur is made up by the addition of water. The sulphurous acid required
for the second operation may be produced by burning a portion of the sulphuretted
hydrogen.

page_text: Improvements in the Production of Sulphur from Sulphuretted
Hydrogen.
We EDWARD William ParseLL and JAMES SIMPSON of 8 Rumford Place Liver-
pool in the County of Lancaster Manufacturing Chemists, 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 :-
==
When sulphuretted Hydrogen is burned with a limited quantity of air in a chamber
lined with brick or other heat retaining material with the object of effecting the
reaction H, S + O HOS and the products of such combustion are cooled it has
been found that the sulphur produced is always far short of the theoretical quantity,
the loss being partly due to the escape in the gaseous form of a mixture of sulpheretted
hydrogen and sulphurous acid and partly to the formation of polythionic acids (mostly
tetrathionic) which to a considerable extent are found mixed with the wet sulphur
mud which is deposited in the cooling chambers. The formation of these thionic acids
we find to be caused by a reverse action between the sulphur originally formed and
the aqueous vapor.
Also when sulphereited hydrogen and sulphurous acid are brought in contact in the
presence of water combination takes place with formation of sulphur and water which
reaction (provided the whole of the sulphur should be found in the solid form) may
be represented by the formula SO2 + 2 H, S = 2 H, O+ 3S but as in the other
reaction above mentioned the product of sulphur is in practice found to fall far short
of the theoretical quantity while polythionic acids mostly tetrathionic are found in the
liquid. The sulphur formed in the latter method of working is not precipitated in
the solid form to any considerable extent, but remains in a quasi soluble condition but
if the acids formed in the liquid be neutralized by a suitable base such as calcium
sulphide the sulphur will separate in the solid form. If the thionic acids or thionates
formed in the said operation are subjected after neutralization to the action of heat
and steam pressure they will be decomposed with precipitation of sulphur and evolution
of sulphurons acid. Further if polythionic acids be allowed to accumulate in a solution
and be subjected for a considerable time to the action of sulpheretted hydrogen
decomposition ensues with formation and precipitation of sulphur.
The object of our invention is (by combining the operation of the first reaction
above mentioned by the hot process in a special manner with the operation of the
second reaction by the liquid process together with a special treatment of the thionic
acids formed) to get a much larger yield of sulphur from a given quantity of
sulphuretted hydrogen than has hitherto been obtained by operating either of the
above mentioned processes separately.
In carrying our invention into practice we burn the sulphuretted hydrogen and air
in any convenient way in a combustion chamber lined with brick or clay and conduct
the hot gases through a chainber filled loosely with brick or other heat retaining
material to a cooling chamber or series of cooling chambers where sulphur will be

page_text: deposited together with some polythionic acids as before mentioned. This method of
producing sulphur from sulphuretted hydrogen is well known having been described
in a provisional Specification filed 15th February 1883 No. 844 by Philip John
Worsley. In adjusting the supply of sulphuretted hydrogen and air to the combustion
chamber we preferably keep the sulphuretted hydrogen in excess as we find that by
so doing the formation of the polythionic acids is considerably reduced.
The gas
escaping from the cooling chamber which contains or has added to it sulphuretted
hydrogen we bring in contact with water containing sulphurous acid in a scrubber or
other convenient apparatus, when sulphur will be formed together with a certain
amount amount of polythionic acids produced in this reaction or already existing in
the gases from the combustion chamber. The liquid so obtained we allow to settle,
the clear liquor containing the thionic acids we return for repeated use in the scrubber
or wash tower. The wet mud mixed with some thionic acids as also the wet sulphur
obtained from the cooling chambers we agitate with calcium sulphide solution or any
suitable alkaline sulphide or base such as milk of lime until the mass shows an alkaline
reaction. The mass so treated we subject to heat and steam pressure in a sulphur
melter or other similar vessel, in the ordinary way in which sulphur is melted. In
this operation the polythionates are decomposed yielding sulphur, sulphurous acid and
under certain conditions sulphuretted hydrogen. The sulphuretted hydrogen evolved
in the before mentioned neutralization of the thionic acids when alkaline sulphides
are employed for the purpose, as also any gases disengaged in the melting operation,
we convey back to any suitable part of the plant where they can be utilized. The
loss incurred by the removal from time to time of liquid froin that used in the wash
tower is made up by the addition of water.
The wash tower as well as all vessels with which the liquid comes in contact before
it is neutralized should be made of wood or of some suitable acid resisting material.
The sulphurous acid necessary for the operation may be conveniently supplied by
burning a small quantity of sulphuretted hydrogen, and passing the products of
combustion into the wash tower. If necessary a little sulphuretted hydrogen may be
introduced in the same manner, the proportion of either being determined by an
examination of the final escaping gases.
Having now. particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed we declare that what we
claim is
First. The process herein described for the production of sulphur from sulphuretted
hydrogen and sulphurous acid consisting 1st in burning sulphuretted hydrogen and
air, 2nd in bringing sulphuretted hydrogen and sulphurous acid in contact in the
presence of water, Brd in separating the sulphur mud produced from the acid water,
4th in neutralizing the said mud with an alkaline reagent, 5th in subjecting the
neutralized mud to heat and steam pressure 6th in utilizing the sulphurous acid and
sulphuretted hydrogen gases evolved substantially in the manner described.
Second. Obtaining sulphur from thionic acids produced in the manufacture of
sulphur from sulphuretted hydrogen in the combined hot and wet processes substantially
as set forth.
Third. The combination of the hot and wet processes of obtaining sulphur from
sulphuretted hydrogen with the decomposition of thionic acids and production of
sulphur substantially as set forth.