Year: 1887

page_text: Date of Application, 25th Apr., 1887
Complete Left, 7th Jan., 1888
Complete Accepted, 20th Apr., 1888
We, WALTER NOEL HARTLEY, of 2, Tabernea Terrace, Monkstown, County Dublin;
Fellow of the Royal Society, Professor of Chemistry in the Royal College of Science,
Dublin, and WILLIAM EDMUND BRANDFORD BLENKINSOP, of Garden Wharf, Church
Road, Battersea, in the county of Surrey, Manufacturing Chemist, do hereby declare
the nature of this invention to be as follows:-
This invention relates to improvements in the manufacture of metallic sulphates
from easily oxidizable metals.
In carrying out this invention we take a metallic oxide of an easily oxidizable metal
such as the binoxido of manganese, or other oxide of manganese, or materials. con-
taining the oxides of manganese as for instance the well known manganese ores,-
pyrolusite, braunite, manganite hausmanite or wad or a manganiferous iron ore or the
material known as recovered manganese obtained in the working of Weldon's process
for the recovery of manganese in the preparation of Chlorine. We mix the manganese
oxide or ore with sulphur or a metallic sulphide, or other sulphurised materials capable
of yielding sulphurous acid gas by the action of heat with or without the joint action
of oxygen; such materials are pyrites, marcasite, galena, blende, factitious pyrites,
coarse metal, spent oxide from gas works, sulphur, polysulphides, thiosulphates, and
excepting sulphites and sulphates, all other compounds or mixtures of sulphur com-
from Alkali Works.
pounds which are found in oxidised "tank waste
In practice we take about 170 parts by weight of binoxide of manganese and about
120 parts of bisulphide of iron or quantities of materials equivalent to these, as for
instance about 17+ parts of manganese ore containing about 98 per cent of the
binoxide of manganese and about 142 parts of pyrites containing about 45 per cent of
We heat the mixture freely
sulphur, both finely ground and intimately mixed.
exposed to the air. The re-action may be carried to a temperature equal to about
that indicated by the dull red heat of iron. The required heat is continued until a
change of colour is observed throughout the mass, caused by the burning of the
pyrites and the change of most of the manganese dioxide into manganese sulphate.
When it is made evident by testing that by further heating no more change can take

page_text: place the mass may be thrown into water and lixiviated. The solution of manganeso
sulphate obtained is practically free from iron or other impurity when made in the
manner described and the pure crystallised salt may be obtained therefrom by the
usual method.
The process of heating is advantageously conducted in an open vessel suitably
covered to prevent radiation of heat, such as an iron pan, an open crucible, a muffle
furnace or a reverberatory furnace employed in tho metallurgical operation of roasting
metallic ores.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Metallic Sulphates.
We, WALTER NOEL HARTLEY, of 2, Tabernea Terrace, Monkstown, county Dublin,
Ireland, Fellow of the Royal Society, Professor of Chemistry in the Royal College of
Scienco, Dublin, and WILLIAM EDMUND BRANDFORD BLENKINSOP, of Garden Wharf,
Battersea, in the county of Surrey, Manufacturing Chomist, 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:-
Our invention consists of improvements in the production of certain metallic.
sulphates from the oxides of easily oxidisable metals such as for instance manganeso
and the metals frequently present therewith in manganese ore such as copper, nickel
and cobalt the sulphates of which are not decomposed at a low red heat.
If it be desired to prepare the sulphate of manganese we tako an oxide of manganese
or an oro or other material containing one or more of the oxides of manganese and we
mix therowith a metallic sulphide such as iron pyrites or any sulphurised materials
capable of yielding sulphurous acid gas when heated in air or of yielding sulphidos or
oxysulphides of manganese or nickel when heated with tho oxides of these inetals in
a closed vessel but we do not use sulphur alone.
We have performed the process with all the substances hereinafter mentioned, that
is to say, with pyrolusite, braunite, manganite, hausmannite and franklinite, all of
which are minerals containing oxides of manganese. Also with wad, manganiferous
iron ores, various manganese ores, carbonate of manganese and the material known as
"Weldon mud" obtained in the working of Weldon's process for the recovery of
manganese in the preparation of Chlorine.
"
The sulphurised materials we have employed are iron pyrites, zinc blende, galena,
coarso metal," copper matt, spent oxide of iron from gas-works, polysulphides,
thiosulphates and the soluble salts from oxidised "tank waste" resulting from the
preparation of alkali by Le Blanc's process.
In our process we do not use clay or flint or other inert material which we have
found not only useless by being without chemical action but also detrimental in
lowering the temperature of the mixture and in impeding the formation of metallic
sulphides or oxysulphides such as the sulphide or oxysulphides of manganese.
The principal chemical change which takes place in our process consists in our
producing sulphide of manganese and the oxysulphides of manganese by heating
pyrites and oxide of manganese mixed together. The sulphide of manganese and
oxysulphides of manganese burn in presence of air and, by their combustion, produce
sulphate of manganese. There remains with the sulphate of inanganese some sulphide

page_text: nits been surjected to a sumerently migh temperature during the last stage of the
operation it is practically free from sulphate of iron and the sulphate of manganese
has been found to contain no iron in sufficient quantity to be detected by the ordinary
chemical tests.
Copper is commonly contained in iron pyrites and nickel and cobalt not unfrequently
occur in manganese ores. When such is the case the sulphates of copper, nickel and
cobalt may be found in the sulphate of manganese. From a solution of sulphate of
manganese the copper, nickel and cobalt may be separated by throwing into the
solution some anhydrous sulphide of manganese or oxysulphile of manganese and
raising the liquid to its boiling point. The sulphates of copper, nickel and cobalt are
thus converted into sulphides while the manganese sulphide goes into solution as man-
ganese sulphate. The insoluble black sulphides of copper, nickel and cobalt are allowed
to settle and the purified solution of manganese sulphate is drawn off.
The sulphide of manganese used in this process may be specially prepared by
heating in a closed vessel such as a crucible a mixture of sulphate of manganese and
powdered coal or charcoal dust in the proportion of 150 parts by weight of sulphate
of manganese and 25 parts by weight of coal. Or instead of specially preparing
sulphide of manganese in the manner just described a portion of a charge of material
prepared from pyrites and manganese ore which is withdrawn from the furnace when
it is in the greenish brown or brown condition and contains the sulphide and oxy-
sulphide of manganese may be thrown into the solution.
The sulphides of copper, nickel and cobalt separated from the solution of manganese
sulphate may be in turn again converted into sulphates by roasting with pyrites and
extracting the roasted material with water.
The copper, nickel and cobalt in solution as sulphates may then, after separating
by subsidence from all insoluble material, be individually separated by any of the well
known methods.
If a charge of materials after withdrawal from the furnace is found to contain
ferrous sulphate it is an indication that the temperature has not been sufficiently high
and in order to remove the iron we mix the cooled product with sufficient water to
yield a stiff mud. We have found the proportion of four gallons of water to
100 pounds weight of the material to be sufficient. The combination of the water
with anhydrous sulphate of manganese causes the mass to become heated.
After exposure to air for some hours it becomes dry and the oxidising action of the
air converts the ferrous sulphate into ferric sulphate. More water is added in order
to form a solution and the solution is boiled which causes an insoluble basic ferric
sulphate to be deposited. The solution of sulphate of manganese freed from iron is
then drawn off from the insoluble matter and evaporated to dryness or to a degree of
concentration at which it will crystallise.
In the manner just described we have remove 14 per cent of ferrous sulphato from
manganese sulphate.
We have removed small quantities of iron from the solution of manganese sulphate
by boiling the solution with some of the brown sulphide or oxysulphide of manganese
removed from the furnace for the purpose as directed for the separation of copper.
We do not limit ourselves to the proportions given in the foregoing description of
our process since we have used with success 166 parts of manganese ore containing
60 per cent of oxide of manganese and 157 parts of pyrites containing 47 per cent of
sulphur.
But we prefer as being more economical the proportions given.
Since the time of filing our Provisional we have made further discoveries of
Improvements in the manufacture of cobalt sulphate and its separation from other
sulphates and for this we have applied for a distinct patent 1887, No. 8922.
°
Having now particularly described and ascertained the nature of our invention and
in what manner the same is to be performed we declare that what we claim is :-
1. The manufacture of sulphate of manganese by heating together an intimate
mixture in a fine state of division composed for the one part of an oxide of manganese

page_text: or ore or other material containing one or more of the oxides of manganese and for
the other part of a metallic sulphide or sulphurised material capable of yielding
sulphurous acid gas when heated in air or of yielding sulphur when decomposed by
heat in a closed vessel substantially as described.
2. The process of separating iron copper, cobalt and nickel from manganese
sulphate by means of an addition of anhydrous manganeso sulphide or oxysulphide to
a solution of the mixed sulphates in the manner describod..
G. F. REDFERN & Co.,
4, South Street, Finsbury, London,
Agents for the Applicants.