Improvements in the Treatment and Reduction of Metallic Ores or Compounds and the Recovery of Metals and Products therefrom.
Year: 1890

page_text: Date of Application, 6th Oct., 1890
Complete Specification Left, 6th July, 1891-Accepted, 22nd Aug., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Treatment and Reduction of Metallic Ores or
Compounds and the Recovery of Metals and Products therefrom.
We, ALFRED JOHN CAMPION of High Cliff Hotel, Cliftonville, Margate, Kent,
Chemist and JOHN EDWARD TENISON-WOODS of No. 263 Camberwell New Road,
London, Civil and Chemical Engineer do hereby declare the nature of this inven-
tion to be as follows:-
Our invention consists of generally: Firstly, in producing hydrogen gas in a
pure and heated state by passing the vapour of heated or superheated steam through
molten metallic iron contained in a closed confined fire resisting vessel. By this
action the steam is decomposed, the oxygen of the water is taken up by the iron
forming the oxide of iron, and the hydrogen gas of the water is liberated in an
uncombined and free and heated state. This hydrogen gas is by suitable outlet
pipes from the closed vessel containing the iron conveyed into a second heated or
fire resisting chamber filled with the oxide or compound of the metal such as
chloride or fluoride of a metal to be reduced.
The temperature of the vessel containing the metallic oxide etcetera is maintained
by a suitable external furnace or heating apparatus to such a heat as will cause the
hydrogen gas to combine with the oxygen fluorine or chlorine in the oxide or
compound under treatment setting the metallic base free in a reduced state as
metal.
When the iron contained in the first named vessel has been completely oxidized
by the steam no further decomposition of water will take place, the steam supply
is then cut off and the pipe connected with a petroleum or other hydro-carbon gas
generator. By this means hydrocarbon gases are passed through the heated oxide
of iron which thereby becomes reduced to its former metallic state.
It is obvious that by this arrangement the production of pure and heated
hydrogen gas can be made alternately without disturbing or renewing the iron
originally placed in the vessel, as it is in this way used over and over again. But
by having two or more vessels containing molten metallic iron as above described
and cach similarly provided with steam pipes and hydro-carbon gas generators the
supply of heated hydrogen gas can be made continuous. The only expenditure in
the process being the petroleum or hydro-carbons used to reduce the oxide of iron
to its former metallic state.
The metals reduced by the action of the heated hydrogen in the second vessel
are tapped off and a fresh supply of the metallic oxide or compound is introduced.
And by using a second reducing vessel the whole operation becomes continuous.
The nature of the reducing crucibles or receptacles in which the metallic oxides
or compounds are subjected to the action of heated hydrogen is a matter of great
importance both as to form and material. We prefer to use generally crucibles
formed in the shapes of ordinary glass pots in common use and for the purposes of
reducing such metals as antimony barium strontium bismuth cadmium cobalt copper
nickel and also all the metals of the platinum group ordinary fire clay or plumbago
crucibles may be used but in reducing compounds of aluminium crucibles should be
employed of the form already described made of powdered emery agglomerated
together by gelatinous alumina. These two substances consist almost wholly of
pure oxide of aluminium, quite infusible, and have the advantage of introducing no
foreign substance or alloy into the aluminium contained in them.
When calcium has to be reduced by our invention the crucibles are preferably
made of lime with or without a small proportion of gelatinous alumina as a binding

page_text: material. This crucible or receptacle is quite infusible at any heat and has the
advantage of introducing no foreign alloy into the calcium metal reduced therein.
In reducing magnesium, crucibles formed and moulded of magnesia would be
used which are infusible and introduce no foreign alloy into the metal.
Manganese may be reduced in a crucible of the same kind as that used for
aluminium, as also can chromium molybdenum titanium tungsten vanadium uranium
and other metals of the earthy group.
Iron may preferably be reduced in crucibles formed of oxide of iron bound
together with a portion of gelatinous alumina. Tin in a crucible formed of oxide
of tin with gelatinous alumina. Zinc in crucibles principally formed of oxide of
zinc and gelatinous silica, and so on with all the metals required to be reduced in
special crucibles where their oxides are infusible until reduced. Lead thalium and
other casily reducible metals whose oxides form strong fluxes can be reduced by our
invention preferably in iron crucibles lined with a mixture of lamp black or
coke or charcoal bound together with refractory alumina in a small quantity.
The non-metallic element boron useful in its pure state for electrical purposes
may be reduced by our invention in crucibles of nearly pure powdered silica as can
also silicon or silesium.
In reducing the oxides or compounds of the alkaline metals such as potassium
sodium lithium etcetera crucibles of iron can be used lined with carbonaceous material
held together by gelatinous alumina.
The second part of our invention consists of methods of treatment and separation
of the sulphides of metallic substances and recovering the constituents thereof.
In treating sulphides of metals for instance iron pyrites which may contain
copper, lead and other metals the material is melted in a small cupola blast furnace
by which process some of the sulphur is driven off and a fused mass of mono-sulphides
accumulates in the well of the furnace in a regulus state which can be run into fire
resisting receptacles previously heated by an external furnace. This receptacle is
provided with a fireclay graphite or fire resisting tube which descends to the bottom
of the receptacle through the melted material through which superheated steam at
a high temperature is passed. The action of the steam in this way decomposes the
sulphides, the oxygen of the water in the steam partly oxidizes the sulphur into
sulphurous acid (SO) and also partly oxidizes the metallic base with which the
sulphur is combined replacing the latter.
The hydrogen in the steam combines with another portion of the sulphur and is
carried off as sulphurated hydrogen gas. The receptacle is closed at the top and
the sulphurous acid and the sulphide of hydrogen (SI) are conveyed into a small
heated chamber by suitable iron or other pipes, there they are mixed with an
equivalent of atmospheric air sufficient to oxidize the sulphur and bydrogen in
the SH forming water and SO, which are conducted over nitrate of soda into
leaden chambers for condensation into sulphuric acid in the usual way. When the
superheated steam has entirely removed the sulphur by its decomposition and has
oxidized the metallic bases the communication with the combustion and the con-
densing chambers is cut off by suitable valves or slides. The material in the
receptacle will be at a very high temperature, as much heat is developed by the
chemical action of the decomposition of the sulphides and elements of steam.
fire resisting tube or tubes which have been used for passing the superheated steam
are connected by means of a two way cock or other suitable means with a vessel
containing boiling crude petroleum or other hydro-carbon. The gas or vapour of
the petroleum so created which has the composition of olifiant gas C, H, passes
through the heated metallic oxides in the receptacle left from the decomposition of
the sulphides as above described and acts upon the same by abstracting the oxygen
from such oxides creating two equivalents of water (HO) and two equivalents
of CO or CO₂ or a mixture of both and the oxides are reduced to the metallic
state.
The
The first action will be on account of elective affinity to reduce any copper lead
or other metals of less oxidizable groups which will be first affected by the action

page_text: of the hydro-carbon gas and the same will accumulate by fusion and gravity at the
bottom of the receptacle as mixed metals principally copper and lead and any
precious metals that may be present which often is the case. The proportion of
lead copper and other easily reducible metals having been ascertained by assay, the
action would be checked at such time as the same are known to be reduced by the
quantity of hydro carbon gas that has been used. The mixed metals are then
tapped off from the tap hole at the bottom of the receptacle and cast into moulds
for subsequent treatment for separation. The material remaining in the receptacle
will now be almost pure sesqui-oxide of iron (FeO3). The external heat of the
receptacle is now increased to the melting point of iron say 2,500 to 3,000 F. degrees
and the petroleum gas by means of the same apparatus is again allowed to pass
through the heated material until the whole of the oxide of iron is reduced to the
metallic state and fused. This melted iron is then tapped off into suitable moulds
and a fresh charge of fused sulphides is run into the receptacle and the above
described operations are repeated. It is important in carrying out this process that
the heat in the receptacle should be maintained at not less than 2000 F. degrees
during the latter period of the process.
In treating sulphides of lead or copper the same process is repeated as above
described for iron pyrites but as already mentioned the crucible or receptacle is
preferably lined with carbonaceous material, otherwise the operation is identical.
In treating the sulphides of the volatile metals such as zinc, antimony, mercury,
gallium and thalium the manipulation is the same as above described for iron until
the whole of the sulphur has been driven off into the condensing chamber but the
reducing receptacle when the hydrogen or hydro-carbon gas is applied to the heated
oxides must be a closed one and provided with an exit pipe leading to an airtight
vessel or chamber in which the metal is condensed. This is also the case when reducing
the oxides of the alkaline metals which are all volatile, and must be condensed in
separate chambers or vessels.
Dated this Sixth day of October 1890.
ALFRED JOHN CAMPION.
JOHN EDWARD TENISON-WOODS.
COMPLETE SPECIFICATION.
Improvements in the Treatment and Reduction of Metallic Ores or
Compounds and the Recovery of Metals and Products therefrom.
We ALFRED JOHN CAMPION of High Cliff Hotel, Cliftonville, Margate, in
the County of Kent, Chemist, and Joux EDWARD TENISON-WOODS of
16 Eastlake Road, Brixton, London in the County of Surrey, Metallurgical
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 :-
Our invention consists of generally in producing hydrogen gas in a pure and
heated state by passing the vapour of heated or superheated steam through molten
metallic iron contained in a closed confined fire resisting vessel. By this action the
steam is decomposed, the oxygen of the water is taken up by the iron, forming the
oxide of iron, and the hydrogen gas of the water is liberated in an uncombined and
free and heated state. This hydrogen gas is by suitable outlet pipes from the
closed vessel containing the iron conveyed into a second heated or fire resisting
chamber filled with the oxide or compound of the metal such as chloride or fluoride
of a metal to be reduced.
The temperature of the vessel containing the metallic oxide etcetera is maintained
by a suitable external furnace or heating apparatus to such a heat as will cause the
hydrogen gas to combine with the oxygen, fluorine, or chlorine in the oxide or
compound under treatment, thus setting the metallic base free in a reduced state
as metal

page_text: When the iron contained in the first named vessel has been completely oxidized
by the steam, no further decomposition of water will take place; the steam
supply is then cut off, and the pipes connected with a petrolcum or other hydro-
carbon gas generator. By this means hydrocarbon gases are passed through the
heated oxide of iron which thereby becomes reduced to its former metallic state.
It is obvious that by this arrangement the production of pure and heated
hydrogen gas can be made alternately without disturbing or renewing the iron
originally placed in the vessel, as it is in this way used over and over again. But,
by having two or more vessels containing molten metallic iron as above described,
and each similarly provided with steam pipes and hydrocarbon gas generators, the
supply of heated hydrogen gas can be made continuous. The only expenditure in
this process is the cost of the petroleum or hydrocarbons used to reduce the oxide
of iron to its former metallic state.
This hydrogen gas thus produced we use in the treatment and reduction of
metallic ores, substances and compounds and recovering the metals and products
therefrom.
The metals reduced by the action of the heated hydrogen in the second vessel arc
tapped off and a fresh supply of the metallic oxide or compound is introduced:
and by using a second reducing vessel the whole operation becomes continuous.
The nature of the reducing crucibles or receptacles in which the metallic oxides
or compounds are subjected to the action of the heated hydrogen in suitable furnaces
is a matter of great importance both as to form and material. We prefer to
use generally crucibles formed in the shape of ordinary glass pots in common use,
and for the purposes of reducing such metals as antimony, barium, strontium,
bismuth, cadmium, cobalt, copper, nickel and also all the metals of the platinum
group, ordinary fire clay or plumbago crucibles may be used; but in reducing com-
pounds of aluminium crucibles should be employed of the form already described
made of powdered emery agglomerated together by gelatinous alumina. These
two substances consist almost wholly of pure oxide of aluminium, quite infusible,
and have the advantage of introducing no foreign substance or alloy into the
aluminium contained in them.
When calcium has to be reduced by our invention, the crucibles are preferably
made of lime with or without a small proportion of gelatinous alumina as a binding
material. These crucibles or receptacles are quite infusible at any practicable heat,
and have the advantage of introducing no foreign alloy into the calcium or other
metal reduced therein.
In reducing magnesium, crucibles formed and moulded of magnesia would be
used, which are infusible, and introduce no foreign alloy into the metal.
Manganese may be reduced in a crucible of the same kind as that used for
aluminium, as also can chromium, molybdenum, titanium, tungsten, vanadium,
uranium, and all other metals of the earthy group.
:
Iron may be preferably reduced in crucibles formed of oxide of iron bound
together with a portion of gelatinous alumina Tin in a crucible formed of oxide
of tin with gelatinous alunina: Zinc in crucibles principly formed of oxide of zine
and gelatinous silica; and so on with all the metals required to be reduced in
special crucibles where their oxides are infusible until reduced. Lead, thalium, and
other easily reducible metals whose oxides form strong fluxes can be reduced by
our invention preferably in iron crucibles lined with a mixture of lampblack, or
pulverized coke, or charcoal bound together with refractory alumina in a small
quantity.
The non metallic element boron useful in its pure state for electrical purposes may
be reduced by our invention in crucibles of nearly pure powdered silica; as can
also silicon or silesium.
In reducing the oxides or compounds of the alkaline metals such as potassium,
sodium, lithium, etcetera crucibles of iron can be used lined with carbonaceous
material held together by gelatinous alumina.
The second part of our invention consists of methods of treatment and separation

page_text: of the sulphides of metallic substances and recovering the constituents thereof. In
treating sulphides of metals, for instance, iron pyrites which may contain copper,
lead, and other metals, the material is melted in a small cupola blast furnace by
which process some of the sulphur is driven off and a fused mass of monosulphides
accumulates in the well of the furnace in a regulus state which can be run into fire
resisting receptacles previously heated by an external furnace. This receptacle is
provided with a fireclay, or graphite, or fire resisting tube which descends to the
bottom of the receptacle through the melted material through which superheated
steam at a high temperature is passed. The action of the steam applied in this
way decomposes the sulphides: the oxygen of the water in the steam partly oxidizes
the sulphur into sulphurous acid (SO) and also partly oxidizes the metallic base
with which the sulphur is combined replacing the latter.
The hydrogen in the steam combines with another portion of the sulphur and is
carried off as sulphurated hydrogen gas. The receptacle is closed at the top and
the sulphurous acid and the sulphide of hydrogen (SH) are conveyed into a small
heated chamber by suitable iron or other pipes. There they are mixed with an
equivalent of atmospheric air sufficiently to oxidize the sulphur and hydrogen in
the SH forming water and SO, which are conducted over nitrate of soda into
leaden chambers for condensation into sulphuric acid (SO,) in the usual way.
When the superheated steam has entirely removed the sulphur by its decomposition
and has oxidized the metallic bases, the communication with the combustion and
the condensing chambers is cut off by suitable valves or slides.
The material in the receptacle will be at a very high temperature, as much heat
is developed by the chemical action of the decomposition of the sulphides and
elements of steam. The fire resisting tube or tubes which have been used for
passing the superheated steam are connected by means of a two way cock or other
suitable means with a vessel containing boiling crude petroleum or other hydro-
carbon. The gas or vapour of the petroleum so created which has the composition
of olifiant gas (CH2) passes through the heated metallic oxides in the receptacle
left from the decomposition of the sulphides as above described and acts upon the
same by abstracting the oxygen from such oxides creating two equivalents of
water (HO) and two equivalents of CO or CO, or a mixture of both, and the
oxides are reduced to the metallic state. The first action will be on account of
elective affinity to reduce any copper, lead, or other metals of the less oxidizable
groups which will be first affected by the action of the hydrocarbon gas, and the
same will accumulate by fusion and gravity at the bottom of the receptacle as mixed
metals, principally copper and lead, and any precious metals that may be present
which often is the case. The proportions of lead, copper, and other easily reducible
metals having been ascertained by assaying, the action would be checked at such
time as the same are known to be reduced by the quantity of hydro-carbon gas that
has been used. The mixed metals are then tapped off from the tap hole at the
bottom of the receptacle and cast into moulds for subsequent treatment for separation.
The material remaining in the receptacle will now be almost pure sesqui-oxide of
iron (FeO). The external heat of the receptacle is now increased to the melting
point of iron, say 2500 to 3000 F. degrees, and the petroleum gas by means of the
same apparatus is again allowed to pass through the heated material until the whole
of the oxide of iron is reduced to the metallic state, and fused. This melted iron
is then tapped off into suitable moulds and a fresh charge of fused sulphides is run
into the receptacle, and the above described operations are repeated.
It is important in carrying out this process that the heat in the receptacle
should be maintained at not less than 2000 F. degrees during the latter period of
the treatment.
In treating sulphides of lead or copper the same process is repeated, as above
described, for iron pyrites, but as already mentioned, the crucible or receptacle is
preferably lined with carbonaceous material, otherwise the operation is identical.
In treating sulphides of the volatile metals such as zinc, antimony, mercury,
gallium, and thalium, the manipulation is the same as above described for iron, until

page_text: the whole of the sulphur has been driven off into the condensing chamber when the
hydrogen or hydrocarbon gas is applied to the heated oxides, but the reducing
receptacles must be a closed one and provided with an exit pipe leading to an air-
tight vessel or chamber in which the metal is condensed. This is also the case
when reducing the oxides of the alkaline metals which are all volatile, and must be
condensed in separate chambers or vessels.
Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is
1. The manufacture of heated hydrogen by the decomposition of steam by passing
the same through molten iron, substantially as set forth.
2. The utilization of the so manufactured hydrogen for the decomposition of
metallic salts and oxides as described.
3. The manufacture of fire resisting crucibles for reducing various metallic oxides
and compounds substantially as set forth.
4. The reduction of the iron used in the manufacture of the heated hydrogen,
which would have become oxidized by means of treating the same at melting
point, and passing through the mass hydro-carbon gas, or gases or vapours sub-
stantially as set forth.
5. The treatment of iron pyrites and other metallic sulphides by passing steam
and air through them in a heated state, and the reduction of the oxides left by
such oxidation as remain by heated hydrogen or by hydrocarbon vapours as
described.
Dated this 6th day of July 1891.
ALFRED JOHN CAMPION.
JOHN EDWARD TENISON-WOODS.