Improvements in the Manufacture of Aluminate of Barium and Aluminate of Strontium, and the Production of Alumina, Sulphate of Barium, and of Strontium, and other Products from the same.
Year: 1896

page_text: Date of Application. 18th Mar., 1896
Complete Specification Left, 19th Nov.. 1996-Accepted, 30th Jan., 1897
Improvements in the Manufacture of Aluminate of Barium and
Aluminate of Strontium, and the Production of Alumina, Sulphate
of Barium, and of Strontium, and other Products from the same.
I, DMITRY ALEXANDROWITCH PÉNIAKOFF of Rue Bauduin Pierre, Huy in the
Kingdom of Belgium, Chemist do hereby declare the nature of my invention to be
as follows:-
The object of this invention is to produce caustic alkalies or alkaline carbonates by
double decomposition between an alkaline sulphate and aluminate of barium or
aluminate of strontium. All that is hereinafter described with reference to barium
is also applicable to strontium. According to the conditions under which the
operation is conducted, there remains in solution either caustic alkali or alkaline
aluminate, while sulphate of barium, mixed with more or less alumina, precipitates.
Sulphate of barium thus obtained may again be employed in the production of
aluminate of barium. I have found in fact, that aluminate of barium forms readily
when a mixture is made of sulphate of barium (or heavy spar) with alumina or
bauxite, or with any metallic sulphide or polysulphide, and the mixture is subjected to.
the action of heat.
There is then evolved sulphurous acid gas which, owing to its purity, may be
utilized with advantage in lead-chambers or, if desired, in Hargreaves process,
chlorine or bydrochloric acid being simultaneously produced.
In the course of calcination of the mixture of alumina, sulphate of barium aud
sulphide (or sulphuret) of barium, the following reaction takes place :-
The bauxite which I have hitherto employed contains a minimum proportion of
silicic acid, and approximately corresponds to the formula 4 A10 + Fe³0. In the
process of calcination, the sesquioxide of iron (FeO3) is for the most part transformed
into protoxide of iron (FeO), so that the whole of the process may he represented by
the two following equations

page_text: several bodies, which are required to make up the mixture whereby the reaction
is to be brought about. In the case of pyrites, however, it should be borne in
mind, that part of the sulphur of the pyrites begins to separate before the reaction
proper commences.
The well-known process of manufacture of aluminate of barium by the calcination
of a mixture of sulphate of barium of bauxite and carbon occasions serious losses of
barium when put in practice, owing to the formation of sulphide (or sulphuret) of
barium, or, in some cases, owing to the double combinations or compounds which
that body forms in conjunction with iron.
Experiments, which I have made in this direction, have shewn that the formation
of these objectionable sulphuretted compounds may be entirely avoided by so
proportioning the quantity of carbon to be employed, that no carbonic oxide
gas (CO) may form. This result may be readily attained by proportioning the
quantities of the several bodies used in accordance with the following equation:-
(4)
2 (4 Al'O + FeO3) + 8 BaSO* + 5 C
- 8 Al'O'BaO+ 4 FeO + 5 CO2 + 8 SO*.
The raw aluminate of barium obtained by either of the two methods is treated
with a solution of alkaline sulphate. A solution of caustic alkali forms which is
almost entirely free from alumina, and all the other elements (sulphate of barium,
alumina and iron oxides) are precipitated. With this precipitate, pyrites or carbon
is mixed in suitable proportions, and in some cases this mixture may be moulded into
blocks and calcined afresh, for the purpose of obtaining aluminate of barium.
The raw aluminate of barium, too, may be washed (lixiviated), in which case the
solution of aluminate of barium, after being separated from the insoluble residues,
is alone treated with the sulphate of an alkali, either in the solid state or in
solution.
According to the temperature, or to the degree of concentration, adopted in
performing this operation, a greater or lesser amount of alumina will be precipitated
at the same time as the sulphate of baryta, whilst the remainder of alumina is in
the condition of alkaline aluminate in solution, whence alumina and alkalies are
extracted which may be done by the well known methods.
The residue (consisting of sulphate of barium and alumina) is treated with acids,
to obtain the corresponding salts of alumina, and the pure sulphate of barium,
which has remained insoluble, may be utilised as a dressing or for other purposes.
Or nearly the whole of alumina may be separated from a solution of aluminate
of either barium or strontium, by maintaining such solution in a state of energetic
agitation in the presence of crystallised hydrate of alumina, or by stirring it by
any suitable mechanical means. There remains in solution either hydrate of barium
or hydrate of strontium, as the case may be, retaining but very little alumina.
It will be observed, moreover, that in carrying out this process, it matters little
whether the alkaline sulphates to be employed be produced in sulphate furnaces, in a
Hargreaves' apparatus or, by the wet process (viz., double decomposition, crystallization
under the action of cold, &c.) as practised at Strassfurt.
Bisulphates may also be used in the performance of this improved process, in which
case the following reaction will ensue.

page_text: Improvements in the Manufacture of Aluminate of Barium and
Aluminate of Strontium, and the Production of Alumina, Sulphate
of Barium, and of Strontium, and other Products from the same.
1, DMITRY ALEXANDROWITCH PÉNIAKOFF of Rue Bauduin Pierre, Huy, in the
Kingdom of Belgium, 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:-
This invention relates to the manufacture of aluminate of barium and aluminate of
strontium, and the production of alumina, sulphate of barium and of strontium and
other products of the same and its principal object is to produce caustic alkalies or
alkaline aluminates by double decomposition between an alkaline sulphate and
aluminate of barium or aluminate of strontium. All that is hereinafter described
with reference to barium is also applicable, to strontium. According to the conditions
under which the operation is conducted, there remains in solution either caustic alkali
or alkaline aluminate, while suiphate of barium, mixed with more or less alumina,
precipitates.
Sulphate of barium thus obtained may again be employed in the production of
aluminate of barium. I have found, in fact, that aluminate of barium forms readily
when a mixture is made of sulphate of barium (or heavy spar) with alumina or
bauxite, and with any metallic sulphide or polysulphide, and the mixture is subjected
to the action of heat.
There is then evolved sulphurous acid gas which, owing to its purity, may be
utilized with advantage in lead-chambers or, if desired, in Hargreaves process,
chlorine or hydrochloric acid being simultaneously produced.
In the course of calcination of the mixture of alumina, sulphate of barium and
sulphide (or sulphuret) of barium, the following reaction takes place :-
(1)
4 A120 +3 BaSO + BaS = 4 ALO³BO+4 SO
The bauxite which I have hitherto employed contains a minimum proportion of
silicic acid, and approximately corresponds to the formula 4 Al2O3 + FeO³."
process of calcination, the sesquioxide of iron (FeO3) is for the most part transformed
into protoxide of iron (FeO), so that the whole of the process may be represented by
the two following equations :-

page_text: I take these formulæ for an exact basis in determining the proportions of the
several bodies, which are required to make up the mixture whereby the reaction is to
be brought about. In the case of pyrites, however, it should be borne in mind
that part of the sulphur of the pyrites begins to separate before the reaction proper
commences.
The well-known process of manufacture of aluminate of barium by the calcination
of a mixture of sulphate of barium of bauxite and carbon occasions serious losses of
barium when put in practice, owing to the formation of sulphide (or sulphuret) of
barium, or, in some cases, owing to the double combinations or compounds which that
body forms in conjunction with iron.
Experiments, which I have made in this direction, have shewn that the formation of
these objectionable sulphuretted compounds may be entirely avoided by so proportioning
the quantity of carbon to be employed, that no carbonic oxide gas (CO) may form.
This result may be readily attained by proportioning the quantities of the several
bodies used, in accordance with the following equation:-
= 8 Al'O'Ba0 + 4 FeO + 5 CO2 + 8 SO'.
The raw aluminate of barium obtained by either of the two methods is treated with
a solution of alkaline sulphate. A solution of caustic alkali forms which is almost
entirely free from alumina, and all the other elements (sulphate of barium, alumina
and iron oxides) are precipitated. With this precipitate, pyrites or carbon is mixed
in suitable proportions, and in some cases this mixture may be moulded into blocks
and calcined afresh, for the purpose of obtaining aluminate of barium.
The raw aluminate of barium, too, may be washed (lixiviated), in which case the
solution of aluminate of barium, after being separated from the insoluble residues, is
alone treated with the sulphate of an alkali, either in the solid state or in solution.
According to the temperature, or to the degree of concentration, adopted in
performing this operation, a greater or lesser amount of alumina will be precipitated
at the same time as the sulphate of baryta, whilst the remainder of alumina is in the
condition of alkaline aluminate in solution, whence alumina and alkalies are extracted
which may be done by the well-known methods.
The residue (consisting of sulphate of barium and alumina) is treated with acids,
to obtain the corresponding salts of alumina, and the pure sulphate of barium,
which has remained insoluble, may be utilized as a dressing or for other purposes.
Or nearly the whole of alumina may be separated from a solution of aluminate of
either barium or strontium, by maintaining such solution in a state of energetic
agitation in the presence of crystallized hydrate of alumina, or by stirring it by any
suitable mechanical means. There remains in solution either hydrate of barium or
hydrate of strontium, as the case may be, retaining but very little alumina.
It will be observed, moreover, that in carrying out this process, it matters little
whether the alkaline sulphates to be employed be produced in sulphate furnaces, in a
Hargreaves' apparatus or, by the wet process (riz:-double decomposition, crystalli-
zation under the action of cold, &c.) as practised at Strassfurt.
Bisulphates may also be used in the performance of this improved process, in which
case the following reaction will ensue :-
(5)
Al2O3BaO+NaHSO A120³ + B₂SONOH

page_text: the calcination of a mixture of sulphate of barium or sulphate of strontium with
materials containing alumina with the addition of either a sulphide compoun: such as
sulphide of iron pyrites sulphide of barium or the like, or carbon in the proportions.
stated, whereby sulphurous acid gas is set free, with the subsequent treatment of the
products obtained, substantially as hereinbefore described.
Dated this 19th day of November 1896.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents..