Year: 1886

page_text: Date of Application, 8th Feb., 1886.
Complete Left, 8th Dec., 1886.
Complete Accepted, 11th Jan., 1887.
1 ALFRED MACDONALD GRAHAM, of 2 Dermody Road, College Park, Lewisham
in the County of Kent, Analytical Chemist do hereby declare the nature of this
invention to be as follows:-
This invention relates to a novel and economical process by means of which metallic
oxides, such for example as binoxide of manganese, or oxide of iron, may be converted
into sulphates, the sulphates thus obtained being applicable for the same uses as
sulphates obtained in an ordinary manner.
In carrying out my invention with reference say to manganese, I take binoxide or
any other oxide of that metal ground to a state of fine powder, and mix with it by
preference bi-sulphide of iron, commonly called iron pyrites, likewise brought to a
state of fine division, or a mixture of sulphur and iron borings (the quantity of sulphur
used should be in excess of the amount required to convert the whole of the manganese
into sulphate). I add to these a porous substance, such for example as dry pulverized
clay, which will allow the free passage of the air through the mass without interfering
with the re-action.-I place this mixture in a converting pan or furnace, to which
atmospheric air is admitted. I apply heat gently at first, and afterwards increase it
gradually. This moderate heating must be continued for some time; generally 7 or
8 hours will be sufficient. The oxidizing action commences at the top, and extends
downwards through the mass, and is usually denoted by some change of color. If
possible, arrangements should be made to withdraw small portions from the mass, so as
to ascertain whether the operation is complete. The contents of the pan or furnace
should on no account be disturbed during the time the heating is continued, as by
shaking, the minute air passages will be closed, and the conversion much retarded.
When the whole of the sulphur has been oxidized, the heat may be still further raised,
and this heating may be continued for two hours.
During the process of heating, the iron pyrites lose a portion of their sulphur, which
is converted by the oxygen of the air into sulphurous acid or anhydride, and forms with
the manganese a soluble sulphate of manganese. Another portion of the sulphurous
acid unites with the iron, forming sulphate of iron. The product thus obtained, when

page_text: mixed with clay in the proportion of about 8 parts sulphate to 92 clay, will be found
to operate very effectually as a sewage precipitant. If, however, the heat, at the close
of the re-action, is raised, the iron is peroxidized, and the acid or anhydride is trans-
ferred to the manganese not previously acted on; or the mixed sulphates may be
dissolved out, and the iron peroxidized by a second operation already known. After
heating for about 9 or 10 hours, the operation may be considered complete; the charge
in the pan or furnace may be allowed to cool, and when sufficiently cold, should be
removed from the pan, moistened with water, and exposed to the atmosphere for more
than a week, at the end of which time the whole of the soluble sulphate of manganese
may be dissolved out by water, and the remaining solid matter examined for manganese.
If any remains unacted on, it may be treated in a subsequent operation.
The oxides of iron, zinc, and other oxides, can be converted into sulphates in the
same way as above described, but the peroxydation of the iron will not then be
necessary.
The oxides of iron or manganese contained in sewage precipitate can be readily
re-converted into sulphates by my process.
The sewage mud is squeezed and dried, and submitted to heat in a furnace, together
with a certain portion of pyrites. The organic matter is vaporized by the heat, and
the oxides are converted into sulphates as already described. The ammonia passing off
in vapour may be arrested in any well known manner.
Thus, the manganese or iron introduced into sewage in the form of sulphate, to effect
precipitation and transformed into oxide by the action of the alkalies, may be recovered
in the form of sulphate, aml used again and again as a precipitate for fresh sewage.
NEWTON & SON,
Agents for the Applicant.

page_text: I ALFRED MACDONALD GRAHAM of No. 2 Dermody Road College Park Lewisham
in the County of Kent Analytical 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 a novel process by means of which the oxides of readily
oxidizable metals such for example as binoxide of manganese or oxide of iron may be
converted into sulphates the sulphates so obtained being applicable for the same uses
as sulphates obtained in an ordinary manner.
In carrying out my Invention with reference say to manganese I take binoxide or
any other oxide of that metal brought to a state of fine division and mix with it by
preference bisulphide of iron commonly called iron pyrites likewise brought to a state
of fine division or sulphur or a mixture of sulphur and iron in a fine state of division
such as iron borings and I add to these either dried clay or flint in a fine state of
division and thoroughly intermix the several matters and place the mixture in an iron
pan or other suitable apparatus and apply a moderate heat say about four hundred or
five hundred degrees Fahrenheit and gradually increase the heat to about the degree
which will produce incipient redness in iron and continue this heat for about seven or
eight hours from the time of starting the heating which is generally sufficient for the
completion of the process. After the process is completed the mixture is allowed to
cool and may then be removed from the pan and moistened with water and exposed to
the atmosphere until the sulphates are rendered soluble which will generally be in about
eight or ten days or a fortnight. The mixed sulphates may then be dissolved out and the
iron peroxidised by well known methods and the remaining solid matter examined for
manganese. If any manganese remain unacted on it may be treated as hereinbefore
described by a further operation.
The action which takes place in the mixture while it is being heated is as follows:-
The sulphur therein is oxidized partially by the oxygen combined with the manganese
and partially by the oxygen of the air entering the mass through the interstices between
the particles of the clay or flint and the resulting sulphurous or sulphuric acid com-
bines with the manganese and with the iron forming sulphate of manganese and
sulphate of iron. The said action begins at the top and extends downwards through
the mixture and is usually denoted by some change of colour.
The quantity of sulphur used in preparing the mixture should be in excess of that
required to convert the whole of the manganese into sulphate which may be ascertained
by analysis of the matters which it may be proposed to use the quantity of sulphur
which will combine with a given quantity of manganese being known. Where iron
pyrites is used the proportion of sulphur contained therein must be ascertained in order
to determine the quantity of pyrites required and allowance must be made for the
quantity which will combine with the iron of the pyrites during the operation. The
quantity of clay or flint required is from about three to five parts by weight thereof to
one part by weight of the oxide.

page_text: In lieu of clay or flint any matter may be used which will not become oxidized by
exposure to heat and which is in a sufficiently fine state of division to allow the passage
of air through the mass to an extent which will not injuriously affect or interfere with
the reaction required. If a matter be used which will admit of too free passage of air
to the mass the sulphur will be burnt and a quantity of the sulphurous acid so formed
will escape from the mass and be lost or wasted and the quantity of sulphate of
manganese or other metallic sulphates resulting from the process will be proportionally
lessened. Where the matter used is of a suitable nature and is in sufficiently fine state
of division there is little or no escape of sulphurous acid from the mass.
The apparatus in which the mixture is heated may be of any kind which will admit
of the necessary heat being applied and of moderate access of air to the mixture while
being heated. A shallow evaporating pan such as is used in the manufacture of salt is
suitable for the purpose. In order to prevent the cooling of the mixture by too free
access of air to the surface thereof it may be loosely covered by metal plates or
otherwise.
The conversion of the oxide into sulphate is much retarted by disturbance of the
mixture while it is being heated therefore this should be avoided as far as possible.
Small portions may however be carefully withdrawn from time to time for testing
without seriously interfering with the action. When little or no odour of sulphurous
acid is perceptible in the portions so withdrawn the process may be considered
complete.
The heat towards the close of the process should not be raised much above the degree
hereinbefore indicated as if raised too much tho iron will be peroxidized.
The oxide of iron and of zinc and oxides of other readily oxidizable metals may be
converted into sulphates by the process hereinbefore described but that part of the said
process which consists of the peroxidation of the iron will of course not then be
necessary.
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 production of sulphates of readily oxidizable metals from their oxides by the
process hereinbefore described which process consists essentially in mixing together the
oxide of the metal of which the sulphate is required and bisulphide of iron or sulphur
and dried clay or flint reduced to a fine state of division or other suitable maiter and
subjecting the mixture to the action of heat until the whole or the greater part of the
sulphur has combined with the oxide.
W. T. WHITEMAN,
Agent for the Applicant.