Year: 1887

page_text: Date of Application, 10th Dec., 1887
Complete Left, 5th June, 1888
Complete Accepted, 6th July, 1888
I, WILLIAM HENRY BECK, of 115 Cannon Street, in the City of London, Consulting
Engineer and Patent Agent do hereby declare the nature of this invention to be as
follows:-
The object of this invention is to utilize the sulphur contained in crude illuminating
gas and in the crude ammoniacal liquor from gas-works for the production of sulphite
and bisulphite of ammonia. This sulphur is taken up by the purifying materials and
has heretofore been lost in most works, having been employed in certain cases only
for the manufacture of sulphuric acid.
In the process forming the subject of the present invention, the ammoniacal liquors
are purified by means of oxide of iron, which removes from them all the sulphur they
contain. This purification is effected by filtering the liquors through the oxide, or by
mixing them therewith and then decanting.
Oxide of iron has already been employed for the purification of crude illuminating
gas, but not, so far as the inventor is aware, for the purification of crude ammoniacal
liquor from gas-works.
The materials which have been used for the purification of the ainmoniacal liquor,
as also those of an analogous character which have been used in the purification of
gas, usually contain about fifty per cent. of free sulphur, and are employed in the
apparatus hereinafter described for the production of sulphurous acid. The ammoniacal
liquors, after having been purified as above described, may be distilled without the
addition of lime, and thus serve for the production of ammonia in the gaseous state.
The two gases thus formed, namely, sulphurous and ammoniacal gases, are conducted
into the apparatus hereinafter described. By their combination they produce a salt
the formula of which is

page_text: The apparatus comprises, firstly,—a suitable apparatus for distilling the ammoniacal
liquor so as to produce dry ammonia which passes off by a pipe. Secondly a furnace
for the production of sulphurous acid by burning or roasting the oxide of iron which
has been used for purifying crude ammoniacal liquors from gas works, or crude
illuminating gas. This furnace may be arranged for burning or roasting either the
purifying materials above described, pyrites, or sulphur. Air is supplied to this
furnace under pressure by means of a fan or any other suitable blowing apparatus.
This fan, or other apparatus capable of drawing and forcing the necessary quantity
of air or gas, may be placed with advantage between the furnace and the tank or vat
where the sulphite of ammonia is to be formed; that is to say, this drawing and
forcing apparatus should be capable of drawing away the sulphurous acid gas formed
by the combustion of the sulphur, and of forcing it into the tank or vat where the
salt is formed. Thirdly, a saturating tank or vat, and fourthly, one or more crystallizing
vats.
The sulphurous acid is conducted from the furnace into a distributor on which are
fixed or formed a series of pipes which pass liquid tight through the bottom of a tank
and rise above the water contained therein. The ends of a series of bent pipes are
passed over the pipes on the distributor so as to form lutes or hydraulic joints in the
aforesaid tank. These bent pipes are perforated with small holes in those parts of
them which are immersed in the liquid in the saturating vat and the sulphurous acid
gas escapes through these small holes into the said vat. The bent pipes are pinched
between and supported by wooden rods fastened together by screws, and the said
pipes can thereby be raised or lowered at pleasure. This arrangement is convenient,
because it enables the apparatus to be put together, or taken to pieces, with
facility.
The ammonia and sulphurous acid gases are conducted by separate pipes under a
pressure of about ten centimetres of water, into the saturating vat containing water.
The two gases combine in this water and form sulphite of ammonia which immediately
dissolves and the liquid becomes heated by the reaction which raises its point of
saturation. When the liquid is saturated in the saturating vat, water is added on the
surface and the heavier saturated liquid is drawn off into the crystallizing vat where
the crystals are deposited by the cooling which then takes place.
The mother liquor is returned to tho saturating vat at the same time as the water
intended to replace that of crystallization. In this way the manufacture is carried on
continuously.
The crystallization may also be effected directly, and the salt collected in the
saturating vat by stopping the action and allowing the saturated liquid to cool, or by
simply allowing the salt crystals to deposit by supersaturation.
The important feature in this new process is that the two gases are introduced at the
same time into a saturated liquid which allows of the immediate crystallization of the
salt formed, without the necessity of having recourse to evaporation.
The delivery of ammoniacal and sulphurous acid gas into the saturating vat is
regulated so that the liquid is always neutral, in order to avoid loss of gas, but the
process may be carried on with alkaline liquors, provided that the excess of alkali is
not too great.
This method of operating avoids the loss of ammonia and sulphurous acid occurring
in those processes which consist either in introducing sulphurous acid into a solution
of ammonia, or in introducing annonia into a solution of sulphurous acid.
In these two cases, the loss of ammonia and sulphurous acid is considerable, and
crystallization can only be effected by evaporation, because it is impossible in practice
to obtain, by these means, a saturated liquid.
By the present invention, crystallized sulphite of ammonia is obtained which may
be transformed, by slow oxidation, in contact with air, into sulphate of ammonia. But
the sulphite of ammonia may be used directly in the arts, and especially as manure in
agriculture, whereby as good and even better results can be obtained than by the use
of sulphate, as it either assimilates more completely, or is transformed in the soil, into
compounds which are assimilable in the highest degree.

page_text: It will be seen that one equivalent of water is liberated.
In the same way that sulphite can be transformed into bisulphite by adding to it
one equivalent of sulphurous acid, so likewise bisulphite may be transformed into
sulphite by adding to it an equivalent of ammonia.
If these two last transformations are made in a suitable volume of water, there will
be formed a considerable quantity of crystals of sulphite without the necessity of
cooling the liquid. In fact the following reactions will take place.
(AI, 250, 10) + 10) + (2 H + NI°)=Z (NIT, DO”, 210).
It is obvious that if one begins with a saturated solution of sulphite, there will be at
the end of the operation twice the quantity of salt in the same volume of liquid
that this volume is capable of dissolving, one half of such salt will therefore be
deposited.
Supposing, for example, that we operate, as in the above case, on quantities corre-
sponding to the chemical equivalents, we shall start with, for example, 67 kilogrammes
of sulphite, which, with 32 kilogrammes of sulphurous acid, will give 90 kilogrammes
of bisulphite with 9 kilogrammes of water. By adding 18 kilogrammes of water and
17 kilogrammes of ammonia, we shall obtain 134 kilogrammes of neutral sulphite.
The quantity of water serving for the solution of the salt, at the beginning of the
operation, not having varied, the formation of these 134 kilogrammes of sulphite will
be effected in a quantity of water which can only dissolve 67 kilogrammes of that
salt and there will consequently be a crystallization or deposit of the remaining
67 kilogrammes of salt.

page_text: It is obvious that the quantity of salt deposited will be less if more water is added
than is strictly necessary for the formation of the salt, and the quantity of salt
deposited may be greater if a smaller quantity of water be added.
The bisulphite of ammonia may be obtained by saturating, with sulphurous acid, a
solution of sulphite of ammonia. On the other hand, the sulphite of ammonia may be
obtained by saturating, with ammonia, a solution of bisulphite of ammonia. These
operations may be effected successively in the same vat, or in separate closed or open
vats.
It may also be observed that before utilizing materials which have been used for
purifying gas and ammoniacal liquor, for the production of sulphurous acid, they may
he treated for the extraction from them of the cyanides, and the ammoniacal salts
they usually contain in considerable quantity.
The processes above described are applicable not only in gasworks but in all
establishments and works in which ammoniacal liquors are produced. In those
establishments and works where purifying materials for coal gas are not employed,
sulphur or pyrites would be burnt or roasted in the furnace to produce the sulphurous
acid gas.

page_text: New or improved Process and Apparatus for the Manufacture of
Sulphite and Bisulphite of Ammonia.
I, WILLIAM HENRY BECK, of 115 Cannon Street, in the City of London, Consulting
Engineer and Patent Agent 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, reference being had to the accompanying sheet
of Drawings and to the letters and figures marked thereon, that is to say :-
The object of this invention is to utilize the sulphur contained in crude illuminating
gas and in the crude ammoniacal liquor from gas works for the production of sulphite
and bisulphite of ammonia. This sulphur is taken up by the purifying materials, and
bas heretofore been lost in most works, having only been employed in certain cases
for the manufacture of sulphuric acid.
In the process forming the subject of the present invention, the ammoniacal liquors
are purified by means of oxide of iron, which removes from them all the sulphur they
contain, This purification is effected by filtering the liquors through the oxide, or by
mixing them therewith, and then decanting.
Oxide of iron has already been employed for the purification of crude illuminating
gas, but not, so far as the inventor is aware, for the purification of crude ammoniacal
liquor from gas works.
The materials which have been used for the purification of the ammoniacal liquor,
as also those of an analagous character which have been used in the purification of
gas, usually contain about fifty per cent. of free sulphur and are employed in the
apparatus hereinafter described for the production of sulphurous acid. The
ammoniacal liquors, after having been purified, as above described, may be distilled
without the addition of lime, and thus serve for the production of ammonia in the
gascous state. The two gases thus formed, namely sulphurous acid and ammoniacal
gases, are conducted into the apparatus hereinafter described. By their combination
they produce a salt the formula of which is
that is to say crystallized bisulphite of ammonia. These salts may be applied directly
to agricultural purposes, or the sulphite may be transformed into sulphate by the
process hereinafter described. •
In the drawings hereto annexed Figure 1 illustrates, in vertical sectional elevation,
the apparatus for manufacturing the sulphite or the bisulphite of ammonia.
The apparatus comprises, firstly, a suitable apparatus a for distilling the ammoniacal
liquor so as to produce dry ammonia which passes off by a pipe a¹. Secondly a

page_text: furnace for the production of sulphurous acid by burning or roasting the oxides of
iron which have been used for purifying crude ammoniacal liquors from gas works, or
crude illuminating gas. This furnace may be arranged for burning or roasting either
the purifying materials above described, pyrites, or sulphur. Air is supplied to this
furnace under pressure by means of a fan c or any other suitable blowing apparatus.
This fan, or other apparatus capable of drawing and forcing the necessary quantity of
air or gas, may be placed with advantage between the furnace and the tank or vat
where the sulphite of ammonia is to be formed; that is to say this air or gas drawing
and forcing apparatus should be capable of drawing away the sulphurous acid gas
formed by the combustion of the sulphur, and of forcing it into the tank or vat where
the salt is formed. Thirdly, a saturating tank or vat d shown in plan in Figure 2,
and fourthly, one or more crystallizing vats e. The sulphurous acid gas is conducted
from the furnace by a pipe 6 into a distributor on which are fixed or formed a
series of pipes which pass liquid-tight through the bottom of a tank k and rise above
the water contained therein. The ends of a series of bent pipes t are passed over the
pipes on the distributor so as to form Intes or hydraulic joints in the aforesaid tank
k. These bent pipes are perforated with small holes in those parts of them which
are immersed in the liquid in the saturating vat d and the sulphurous acid gas escapes
through these small holes into the said vat d. The bent pipes t are pinched between
and supported by wooden rods a fastened together by screws, and the said pipes can
thereby be raised or lowered at pleasure. This arrangement is convenient because it
enables the apparatus to be put together or taken to pieces with facility.
The ammonia and sulphurous acid gases are conducted by separate pipes a¹ and b¹
under a pressure of about ten centimetres of water, into the saturating vat d containing
water. The two gases combine in this water and form sulphite of ammonia which
immediately dissolves, and the liquid becomes heated by the reaction; this rise in
temperature raises the point of saturation of the liquid. When the liquid is saturated
in the saturating vat d, water is added on the surface and the heavier saturated liquid
is drawn off through the pipe h into the crystallizing vat e, where the crystals are
deposited by the cooling which then takes place.
The mother liquor is returned to the saturating vat d at the same time as the water
intended to replace that of crystallization. In this way the manufacture is carried on
continuously.
The crystallization may also be effected directly, and the salt collected in the
saturating vat d by stopping the action and allowing the saturated liquid to cool, or by
simply allowing the salt crystals to deposit by supersaturation.
The important feature in this new process is that the two gases are introduced at
the same time into a saturated liquid which allows of the immediate crystallization of
the salt formed, without the necessity of having recourse to evaporation.
The delivery of ammoniacal and sulphurous acid gas into the saturating vat is
regulated so that the liquid is always neutral, in order to avoid loss of gas; but the
process may be carried on with alkaline liquors provided that the excess of alkali is
not too great.
This method of operating avoids the loss of ammonia and sulphurous acid occurring
in those processes which consist either in introducing sulphurous acid into a solution
of ammonia, or in introducing ammonia into a solution of sulphurous acid. In both
these cases the loss of ammonia and sulphurous acid is considerable, and crystallization
can only be effected by evaporation, because it is impossible in practice to obtain by
these means, a saturated liquid.
By the present invention crystallized sulphite of ammonia is obtained which may be
transformed, by slow oxidation, in contact with air, into sulphate of ammonia. But
the sulphite of ammonia may be used directly in the arts, and especially as manure in
agriculture, whereby as good, and even better, results can be obtained than by the use
of sulphate as the sulphite either assimilates more completely, or is transformed, in the
soil, into compounds which are assimilable in the highest degree.
The reactions may be effected, if preferred, in closed vessels by arranging several
closed saturating vats one after the other. In this manner the gases which are not

page_text: absorbed in the first vat would be absorbed in the second, those not absorbed in the
second would be absorbed in the third and so on.
The advantages resulting from the process and apparatus above described may be
summarised as follows:
1. The purification of the ammoniacal liquors by the use of oxide of iron, which
enables such liquors to be distilled subsequently without the addition of lime.
2. The utilization of the sulphur contained in materials which have been used in the
purification of the ammoniacal liquors and of gas, which materials may be employed
again for the purification of ammoniacal liquors and of gas, after the sulphur they
contain has been burnt out of them.
3. The production, by a simple and inexpensive apparatus, of a white crystallised
ammoniacal salt, which may be used directly as manure in agriculture; for the
production of sulphurous acid, and for the production of cold as the solution of the
salt in an equal weight of water produces a reduction of temperature of 15°
centigrade.
With the same apparatus and by the same processes bisulphite of ammonia may be
manufactured which has the following chemical formula --
To produce bisulphite, it is only necessary to conduct the sulphurous acid and
ammonia gases into the saturating vat d in proper proportions, namely one equivalent of
ammonia to two equivalents of sulphurous acid; or to conduct the sulphurous acid
into a solution of sulphite. In the latter case the following reaction will take place
5 namely :-
in which it will be seen that one equivalent of water is liberated.
In the same way that sulphite can be transformed into bisulphite by adding to it
one equivalent of sulphurons acid, so likewise bisulphite may be transformed into
sulphite by adding to it an equivalent of ammonia.
If these two last transformations are made in a suitable volume of water, there will
be formed a considerable quantity of crystals of sulphite without the necessity of
cooling the liquid. In fact the following reactions will take place :-
1º. NH³, SO, 2 HO + SO2 = NH³, 2 SO2, HO + HO
2°. ((NH3, 2 SO, HO) + HO) + (2 HO + NH3) = 2 (NH, SO, 2 HO)
It is obvious that if we begin with a saturated solution of sulphite, there will be at
the end of the operation twice the quantity of salt in the same volume of liquid that
this volume is capable of dissolving, one half of such salt will therefore be deposited.
Supposing for example, that we operate, in the above case, on quantities corre-
sponding to the chemical equivalents, we shall start with, for example, 67 kilogrammes
of sulphite which, with 32 kilogrammes of sulphurous acid, will give 90 kilogrammes
of bisulphite with 9 kilogrammes of water. By adding 18 kilogrammes of water and
17 kilogramines of ammonia, we shall obtain 134 kilogrammes of neutral sulphite.
The quantity of water serving for the solution of the salt, at the beginning of the
operation, not having varied, the formation of these 134 kilogrammes of sulphite will
be effected in a quantity of water which can only dissolve 67 kilogrammes of that salt
and there will consequently be a crystallization or deposit of the remaining 67 kilo-
grammes of salt.
It is obvious that the quantity of salt deposited will be less if more water is added
that is strictly necessary for the formation of the salt, and the quantity of salt deposited
may be greater if a smaller quantity of water be added.

page_text: which contains two equivalents of water of combination, is desiccated so as to deprivo
it of one equivalent of water; it is then put into heaps. In this condition it absorbs
oxygen from the air very rapidly even in the interior of the heap; the reaction is so
violent that the mass of salt becomes heated to a temperature which reaches, and even
exceeds 100 degrees Centigrade. So that to avoid decomposition of the salt, which
takes place at an excessive temperature, it must be spread out in tolerably thin layers.
These two operations, desiccation and oxidation, may be effected in the open air if care
be taken not to allow the salt to reach, or exceed, the temperature of decomposition,
which is indicated by the odour of ammonia. But these two operations of desiccation
and oxidation may be effected in closed spaces or vessels, so as to allow of the collection
of the small quantities of ammonia that may be liberated, and of their utilization again
in the manufacture of sulphite by passing them into the saturating vat or washers.
And to avoid too great a rise of temperature during the oxydizing process in a close
vessel, the quantity of air admitted thereto may be limited.
The bisulphite of ammonia may be obtained by saturating, with sulphurous acid, a
solution of sulphite of ammonia. On the other hand the sulphite of ammonia may be
obtained by saturating, with ammonia, a solution of bisulphite of ammonia. These
operations may be effected successively in the same vat or in separate closed or open
vats.
It may
also be observed that before utilizing the materials which have been used
for purifying gas and ammoniacal liquor, for the production of sulphurous acid, they
may be treated for the extraction from them of the cyanides, and the ammoniacal salts
they usually contain in considerable quantity.
The processes above described are applicable not only in gas works but in all
establishments and works in which ammoniacal liquors are produced. In those
establishments and works where purifying materials for coal gas are not employed
sulphur or pyrites would be burnt or roasted in the furnace to produce the sulphurous
acid gas.
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 :-
First The process for removing sulphur from ammoniacal liquors which consists in
passing or filtering such liquors through, or mixing them with, oxide of iron, as
hereinbefore described.
Second The process for producing sulphurous acid gas which consists in burning or
roasting oxide of iron saturated with sulphur, as hereinbefore described.

page_text: Third The process for producing dry or gaseous ammonia which consists in distilling,
without the addition of lime, ammoniacal liquor purified by oxide of iron, as herein-
before described.
Fourth The process for producing sulphite or bisulphite of ammonia which consists
in the introduction of sulphurous acid and ammoniacal gases together into a saturated
solution, whereby such sulphite or bisulphite of ammonia is produced without
evaporation, as herein before described.
Fifth The use of oxide of iron for removing the sulphur contained in crude
ammoniacal liquors as hereinbefore described.
Sixth The apparatus hereinbefore described, and illustrated in the Drawings hereto
annexed, for the purpose of producing crystallized sulphite or bisulphite of ammonia
from purified ammoniacal liquors and the sulphur resulting from the purification of
such liquors, or of illuminating gas, or from pyrites, or other sources.
Seventh The application and use of gas washing apparatus for the purpose of
effecting the absorption of sulphurous acid by neutral sulphite of ammonia as herein-
before described.
Eighth The processes for producing bisulphite of ammonia by saturating a solution
of sulphite of ammonia with sulphurous acid, and for producing sulphite of ammonia
by saturating a solution of bisulphite of ammonia with ammonia as hereinbefore
described.
Ninth The application and use of sulphite or of bisulphite of ammonia for the
purpose of manure, or for producing sulphurous acid, and for cooling, as hereinbefore
described.
Tenth The process for transforming sulphite of ammonia into sulphate of ammonia,
by desiccation and subsequent oxidation in the open air or in closed vessels, as
hereinbefore described.