Improvements in the Manufacture or Production of Aluminates and of Sulphurous Acid
Year: 1895

page_text: Date of Application, 19th Nov., 1895
Complete Specification Left, 24th July, 1896-Accepted, 19th Sept., 1896
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Aluminates and
of Sulphurous Acid.
I DMITRY ALEXANDROWITCH PÉNIAKOFF, of Rue Bauduin Pierre, Huy in
the Kingdom of Belgium, Chemist, do hereby declare the nature of this invention
to be as follows:-
Alkaline aluminates, or aluminates of the alkaline earths are formed by the
action of sulphates upon alumina in the presence of sulphides, in accordance with
the following formulæ :-

page_text: It contains 60 per cent. of alumina and 24 per cent. of oxide of iron. With these
ores the whole process, and the proportions in which the intervening agents are to
be used may be approximately expressed by the following formulæ :-
(4) 3 (AO)FеО¸ + 12 NaSO4 + 5 FeS = 12 Al,O,Na₂O + 17 SO, + 11 FeO.
(5) (Al₂O) Fe₂O3 + 4 Na2SO4 + FeS2 4 Al₂O₂Na,O + 6 SO, + 3 FeO.
=
In the aluminous ore, the iron is mainly present in the form of sesquioxide of
iron (Fe,O) while in the final product of calcination it assumes for the most part
the form of oxide (FeO). It is therefore obvious that this transformation is
brought about at the expense of the sulphur of the sulphides employed. Never-
theless the sulphnr is not lost, for it will be yielded in the form of sulphurous
acid (SO,).
Another important factor is the degree of hydration of the raw material
employed. The action of steam upon metallic sulphides is well known. The
evaporation of water may partly facilitate the dissociation of the sulphides
employed, and on the other hand, cause hydro-sulphuric acid to be formed; there
being a possibility in either case of a certain amount of sulphur being lost or made
unavailable for the operation. Therefore either the materials to be mixed for
calcination should be de-hydrated beforehand, or a certain surplus of sulphides
should be added in proportion corresponding to the loss of sulphur likely to be
sustained.
In the reactions hereinbefore described, the calcareous matter frequently met
with in aluminous ores, act the same part as iron oxides, and the sulphides and
poly-sulphides of sodium and iron may in the process according to this invention
be replaced by other metallic sulphides.
The sulphurous acid (extremely concentrated and mixed with the strictly
necessary quantity of air) which is disengaged in these re-actions can be as in my
process described in the Specification of Letters Patent No. 20604 of 1893, very
conveniently utilized for transforming alkaline chlorides or chlorides of the alkaline
earths into the corresponding sulphates and chlorine or hydrochloric acid.
The production of chlorine is rendered much easier by using instead of
atmospheric air, the well known oxygen yielding compounds.
Dated this 19th day of November 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture or Production of Aluminates and
of Sulphurous Acid.
I, DMITRY ALEXANDROWITCH PÉNIAKOFF of Rue Bauduin Pierré 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 :-
Alkaline aluminates or aluminates of the alkaline earths are formed by the
action of sulphates upon alumina in the presence of sulphides in accordance with
the following formula
(1) 4 AO, +3 Na₂SO, + Na,S = 4 Al₂OзNa₂O + 4 SO,
(2) 3 Al₂O3 + 3 Na₂SO, + FeS = 3 Al,O,Na2O + 4 SO₂ + FeO

page_text: The sulphur chiminated in the early stage of the main reaction is wasted
unavailable for the operation as a reducing medium, inasmuch as only a small
portion of that sulphur, as it is converted into vapour, has an opportunity of
converting sulphate into sulphide.
These facts have to be taken into consideration whenever disassociable poly-
sulphides are operated upon for it is then that a reaction sets in, in accordance
with the following formula :-
unavailable for the operation as a reducing medium, inasmuch as only a small
portion of that sulphur, as it is converted into vapour, has an opportunity of
converting sulphate into sulphide.
These facts have to be taken into consideration whenever disassociable poly-
sulphides are operated upon for it is then that a reaction sets in, in accordance
with the following formula
11
(3) 3 Al₂O, +3 Na₂SO4 + FeS2 = S + 3 Al₂ON₁₂O + 4 SO, + FeO.
and therefore before the reaction commences the greater part of the disassociable
sulphur is already eliminated.
These conditions however are changed if, instead of pure alumina, aluminous
ore, more or less rich in oxide of iron, be employed in the operation.
In this case the sulphur eliminated from the polysulphide, instead of being lost,
-as it is when pure alumina is operated upon,-combines in a great proportion
with the oxide of iron, and in so doing, forms a mono-sulphide of iron, in which
form it remains fixed in the mass or material under treatment. This being so, if
the operation were conducted with any reference to the proportions indicated in
the formula No. 3, sulphur in excess, would be obtained, which would be retained
by the final product of calcination, in the state of sulphide and in consequence
there would be a disturbance in the reaction and the formation of an impure
product. As the aluminous ores, as generally used, mostly contain a greater or
less proportion of oxide of iron, their richness in this respect becomes, in the
process according to this invention a feature essential for determining the
proportions in which the sulphurous products should be used.
The aluminous ore which I preferably employ is red bauxite, containing but
little silica, and the composition of which may be expressed with approximate
accuracy by the following formula :-
:-
whole process, and the proportions in which the intervening agents are to be used,
may be approximately expressed by the following formula:-
(4) 3 (AO)FeO3 + 12 Na₂SO, + 5 FeS = 12 Al,O,Na,O + 17 SO, + 11 FeO.
(5) (AO)FеО + 4 Na,SO, + FeS, = 4 Al,O,Na,O + 6 SO, + 3 FeO.
3
In the aluminous ore, the iron is mainly present in the form of sesquioxide of
iron (FeO3); while in the final product of calcination, it assumes for the most
part the form of oxide (FeO). It is therefore obvious that this transformation
is brought about at the expense of the sulphur of the sulphides employed.
Nevertheless the sulphur is not lost, for it will be yielded in the form of sulphurous
acid (SO,).
The
Another important factor is the degree of hydration of the raw material
employed. The action of steam upon metallic sulphides is well known.
evaporation of water may partly facilitate the dissociation of the sulphides
employed and, on the other hand, cause hydro-sulphuric acid to be formed; there
being a possibility, in either case of a certain amount of sulphur being lost or
made unavailable for the operation. Therefore either the materials to be mixed
for calcination should be de-hydrated beforehand, or a certain surplus of sulphides
should be added, in proportion corresponding to the loss of sulphur likely to be
sustained.
In the reactions herein before described, the calcareous matters frequently met
with in aluminous ores, act the same part, as iron oxides; and the sulphides and

page_text: poly-sulphides of sodium and iron, may in the process, according to this invention
be replaced by other metallic sulphides.
The sulphurous acid (extremely concentrated and mixed with the strictly
necessary quantity of air) which is disengaged in these reactions can be, as in my
process described in the Specification of Letters Patent No. 20604 of 1893 very
conveniently utilized for transforming alkaline chlorides or chlorides of the alkaline
earths into the corresponding sulphates and chlorine or hydrochloric acid.
The production of chlorine is rendered much easier by using instead of
atmospheric air the well known oxygen yielding compounds.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed I declare that what
I claim is
The manufacture of aluminates simultaneously with the production of sulphurous
acid by the calcination of an intimate mixture of alkaline sulphates or sulphates
of the alkaline earths with aluminous ores or the like and any metallic sulphide in
or about the proportions herein before indicated.
Dated this 24th day of Jul, 1806
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.