CERTAIN IM- PROVEMENTS IN THE PRODUCTION OF METALS OR METALLIC ALLOYS, AND IN THE PROCESS EMPLOYED THEREFOR
Year: 1877

page_text: LETTERS PATENT to John Hollway, of the Firm of Hollway, Brothers, of 7,
Jeffrey's Square, in the City of London, for the Invention of "CERTAIN IM-
PROVEMENTS IN THE PRODUCTION OF METALS OR METALLIC ALLOYS, AND
IN THE PROCESS EMPLOYED THEREFOR."
Sealed the 17th July 1877, and dated the 20th January 1877.
PROVISIONAL SPECIFICATION left by the said John Hollway at the Office
of the Commissioners of Patents on the 20th January 1877.
"
JOHN HOLLWAY, of the Firm of Hollway, Brothers, of 7, Jeffrey's Square, in the
City of London. CERTAIN IMPROVEMENTS IN THE PRODUCTION OF METALS OR
METALLIC ALLOYS, AND IN THE PROCESS EMPLOYED THEREFor."
This Invention relates to improvements in the production of metals and metallic
alloys other than ferro-manganese and Spiegel eisen. Letters Patent were granted
to me on the 5th day of April, 1876, No. 1446, for the Manufacture of Spiegel Eisen
or Ferro-manganese, and on the 23rd of August, 1876, a Patent, No. 3314, was
accorded me for an Invention the primary object of which was the utilisation of a
substance commonly called blue billy," or purple ore.
"
This present Invention relates to the production of metalliferous compounds by a
similar process to that described in the Specifications of the Patents above referred
to, but inasmuch as the production of the metalliferous compounds forming the
subject of this Invention is intended for the manufacture of specific qualities of
metals or alloys other than Spiegel eisen or ferro-manganese and the utilisation of
metalliferous substances, in powder or otherwise, difficult of reduction, I will
describe as embraced by these present improvements, the production of metalliferous
compounds out of various kinds of ores or other metalliferous substances herein-
after more particularly referred to combined with carboniferous and other substances,
which when smelted will produce the specific metal or inetallic alloy.

page_text: One of my objects in the development of this Invention is the formation of a
compound metallic coke containing as ingredients substances known as oxide of
chromium and oxide of iron, which coke when smelted will produce ferro-chromium
or chromeisen.
Another object is the formation of a compound metallic coke containing, in
addition to oxides of iron and chromium, substances containing manganese, for the
production of an alloy of chromium, manganesium, and iron. These will serve as
examples for other alloys, and by my process I overcome the difficulties which have
heretofore been obstacles to the smelting of chrome and other ores which cannot be
readily smelted.
It is very difficult, if not impossible, to reduce chrome iron ores in the ordinary
blast furnace or by other ordinary methods for the following reasons:-
First. Chrome ores are generally found in very compact masses.
Second. Sesquioxide of chromium, the oxide of chromium generally found
associated with protoxide of iron, retains its oxygen with great tenacity.
These oxides are not easily reduced by the action of carbonic oxide, but are
more easily acted on by carbon in intimate contact. The protoxide of iron is,
probably, first reduced to the metallic state, and then assists in smelting the oxide
of chromium.
Third. Chrome ores frequently do not possess in sufficient quantities the neces-
sary ingredients for a good slag, lime and other suitable components being often
deficient.
To overcome these obstacles and so produce ferro-chromium, I take chrome iron
ore, adding thereto iron ore, if desired, with the fluxes necessary, together with
sufficient coal or other carbonaceous materials, and bitumen, if necessary, to make
a sound coke, pulverise or disintegrate and wash the ingredients that require to be
so treated, and well mix the whole. The mixture when coked and smelted alone or
with suitable metalliferous substances, and with or without ordinary coke, will be
capable of yielding ferro-chromium or chromeisen.
To produce an alloy of chromium, manganesium, and iron, I take substances con-
taining manganese, chromium, and iron, with the necessary fluxes if desired,
together with sufficient coal, adding bitumen if necessary to make a sound coke,
pulverise or disintegrate and wash such of the ingredients as require to be so treated,
and well mix the whole. The mixture when coked and smelted alone, or with
suitable metalliferous substances and with or without ordinary coke, will yield an
alloy of chromium, manganesium, and iron.
The following will serve as an illustration of the manner in which by the same
process residues and substances containing metals, and especially those of small
commercial value, may be utilised in an economical manner by their admixture
with coal or other carbonaceous materials, and bitumen if required, and other sub-
stances as herein-after described:
-

page_text: This when smelted with iron ores with or without ordinary coke will produce
pig iron. The above proportions of materials are not arbitrarily fixed, nor is it
suggested that they should all be employed to form the compound, the foregoing
example being an extreme case, given for the purpose of shewing that a careful
study of the analyses of various substances will enable the operator to use and
blend them advantageously one with the other, both as regards quantities, qualities,
and cost.
The ingredients should be varied according to the different characters and
analyses of the metalliferous substances to be smelted with the metallic coke,

page_text: If the coking is not done prior to the introduction of the mixture into the blast
furnace, it will be necessary to form it into lumps or bricks which will hold to-
gether while coking in the furnace.
I am cognizant of the fact that several attempts have been made to deal with
ferreous substances in powder by mixing them with coal, and even bitumen, and
coking them, or making them into blocks; but these have never been brought to a
successful issue, because the intention having been to smelt the mixture alone, it
was considered important to produce coke or blocks containing the largest possible
per-centage of metal as compared with the per-centage of carbon, or that the carbon
contained in the coke should not be in excess of the quantity required for the
reduction of the metallic oxides also contained therein; the resulting product was
therefore unfit for use in a blast furnace, and the attempts to carry on the process
have been abandoned.
. As the pitch or other bituminous matter is added, principally for the purpose of
making the coke or blocks sound, the quantity used (if any) must depend on the
quality of the coal or other carboniferous materials used.
I have ascertained that in order to make sound metallic coke, it is necessary that
it should contain an excess of carbon beyond what is required to smelt the metal-
liferous substances in the mixture, and to smelt it economically, additional
metalliferous substances must be smelted therewith in order to utilise this excess.
This can be done with or without an additional quantity of ordinary coke.
When utilising and smelting substances of small value, the economy of carbon is
of vital importance, whereas when producing specific metallic alloys, or sinelting
metalliferous substances difficulty of reduction, it may be advisable to employ the
excess of carbon, in order to facilitate the reduction of the metalliferous substances.
This process is peculiarly adapted for the production of metallic compounds or
alloys such as ferro-chromium and iron alloyed with chromium and manganesium,
as in the examples given; or iron alloyed with titanium, tungsten, or other metals,
as the relative proportions of metals in the mixture can be very easily controlled,
thus enabling the operator to produce definite alloys.
In addition to these advantages, the intimate and close admixture of the metal-
liferous with the carboniferous and other substances facilitates the smelting,
especially in the case of metallic oxides which are difficult of reduction.
Further, the ingredients being in a pulverulent state, objectionable constituents
can be more easily removed by washing or other purifying processes; for example,
ores containing phosphorus, after being pulverised, can be washed to get rid of the
fossil remains which are found in aqueous iron ore deposits, and these as well as
other iron ores can, if desired, be treated with sulphurous or other acids for the
purpose of further reducing the per-centage of phosphorus, thus rendering it
suitable for the manufacture of the better qualities of iron and steel.
This
pulverulent condition of metalliferous substances has heretofore been considered a
mechanical difficulty; in order to overcome this many processes have been devised.
In my process, however, this condition is an advantage, if not even a necessity.
When non-coking coal, or other carbonaceous material is used, or metalliferous
substances which are reducible at a temperature which renders coking only partially
or altogether unnecessary, it will be advisable to mix the ingredients together, in a
heated state preferred, and form them into blocks by pressure, taking care to use
sufficient binding materials, particularly bitumen, in order that the blocks may hold
together. These blocks may be baked and partially or wholly coked before intro-
duction into the furnace, and if not wholly coked the coking and smelting will be
completed in the furnace.
It will be understood that the reasons why I have not definitely described the
quantities of the various ingredients proposed to be mixed in the production of the
metalliferous compounds is owing to the fact that the ingredients to be treated vary
so much in their components; for example, metalliferous substances, the fluxes, and
even ores from the same mine, are found to differ considerably in their analyses,
and the same remark also applies to coal and other carboniferous substances, there-

page_text: fore the proportions of such ingredients must be regulated by their analyses or
bituminous qualities, and by the analyses of the metalliferous substances intended
to be used with the metallic coke, as will be well understood by persons experienced
in smelting metals.
I may mention as some of the advantages of my process,-
Firstly. The disintegration of the various materials employed; (a) renders it
possible to remove objectionable matter by washing or other means; (b) renders
the reduction more facile, owing to the particles of oxides or metalliferous substances
being brought into direct contact with carbon, and the silica being also brought
into similar direct contact with the bases necessary for fusion. Hence a smaller
quantity of metal is lost in the slag.
.
Secondly. The various substances can be arranged in the mixture, so that any
deficiency or excess of any of the constituents can be compensated.
Thirdly. Many oxides, such as those of chromium, titanium, cerium, manganese,
and others, resist the action of carbonic oxide at even a high temperature, and are
yet reducible by intimate contact with carbon and metallic iron.
Fourthly. In coking the mixture a chemical action takes place, and the particles
are brought into very close contact with each other.; the mixture is swollen by the
heat, and the hydrocarbons evolved pass through the mass, and deposit part of their
carbon in the interstices of the metallic oxides, thus materially assisting the after
reduction of the oxides.
Fifthly. Ecomony in consumption of carbon.-A much larger proportion of
carbon is used in the reduction of oxides than is theoretically necessary.
The following are some of the reasons for the economy of my process:-
(a). The iron in the metallic coke, being in a state of protoxide, requires less
carbon for the purpose of reduction than it would if in the form of peroxide.
(b). The oxides in the coke being reduced by direct contact with carbon, the
reduction would probably be effected almost with the theoretical amount of carbon
necessary.
(c). The ogygen from the oxides in the coke, combining of necessity with the
carbon, will assist in the reduction of the additional ores added to the charge of
metallic coke, and the excess of carbon in the coke will serve for the same purpose
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said John Hollway in the Great Seal Patent Office on the 20th July
1877.
JOHN HOLLWAY, of the Firm of Hollway, Brothers, of 7, Jeffrey's Square, in the
City of London. "CERTAIN IMPROVEMENTS IN THE PRODUCTION OF METALS OR
METALLIC ALLOYS, AND IN THE PROCESS EMPLOYED THEREFOR."
The Invention relates to improvements in the production of metals and metallic
alloys other than ferro-manganese and Spiegel eisen, Letters Patent were granted to
me on the 5th day of April, 1876, No. 1446, for the manufacture of Spiegel eisen
or ferro-manganese, and on the 23rd of August, 1876, No. 3314, a Patent was
accorded to me for an Invention, the primary object of which was the utilisation of
a substance commonly called "blue-billy" or purple ore.
This present Invention relates to the production of metalliferous compounds by a
similar process to that described in the Specifications of the Patents above referred to,
but inasmuch as the production of the metalliferous compounds forming the subject
of this Invention is intended for the manufacture of specific qualities of metals or
alloys other than Spiegel eisen or ferro-manganese, and the utilisation of metalliferous
substances in powder or otherwise difficult of reduction. I will describe as embraced
by these present improvements the production of metalliferous compounds out of
various kinds of ores or other metalliferous substances herein-after more particularly

page_text: referred to combined with carboniferous and other substances which, when smelted,
will produce the spacific metal or metalic alloy.
One of my objects in the development of this Invention is the formation of a
compound metallic coke containing as ingredients substances known as oxide
of chromium and oxide of iron, which coke when smelted will produce ferro-
chromium or chromisen.
Another object is the formation of a compound metallic coke containing, in
addition to oxides of iron and chromium, substances containing manganese for the
production of an alloy of chromium, manganesium, and iron. These will serve as
examples for other alloys, and by my process I overcome the difficulties which have
heretofore been obstacles to the smelting of chrome and other ores which cannot be
readily smelted.
It is very difficult, if not impossible, to reduce chrome iron ores in the ordinary
blast furnace or by other ordinary methods, for the following reasons:-
First. Chrome ores are generally found in very compact masses.
Second. Sesquioxide of chromium, the oxide of chromium, generally found
associated with protoxide of iron, retains its oxygen with great tenacity. These
oxides are not easily reduced by the action of carbonic oxide, but are more easily
acted on by carbon in intimate contact. The protoxide of iron is probably first
reduced to the metallic state, and then assists in smelting the oxide of chromium.
Third. Chrome ores frequently do not possess in sufficient quantities the necessary
ingredients for a good slag, lime and other suitable components being often eficient.
To overcome these obstacles, and so produce ferro-chromium, I take chrome iron
ore, adding thereto iron ore, if desired, with the fluxes necessary, together with
sufficient coal or other carbonaceous materials, and bitumen, if necessary, to make a
sound coke, pulverise or disintegrate and wash the ingredients that require to be so
treated, and well mix the whole. This mixture when coked and smelted alone or
with suitable inetalliferous substances, and with or without ordinary coke, will be
capable of yielding ferro-chromium or chromeisen.
To produce an alloy of chromium, manganese, and iron, I take substances con-
taining manganese, chromium, and iron, with the necessary fluxes, if desired,
together with sufficient coal, adding bitumen, if necessary, to make a sound coke;
pulverize or disintegrate, and wash such of the ingredients as require to be so
treated, and well mix the whole. The mixture, when coked and smelted alone or
with suitable metalliferous substances, and with or without ordinary coke, will
yield an alloy of chromium, manganese, and iron.
The following will serve as an illustration of the manner in which, by the same
process, residues and substances containing metals, and especially those of small
commercial value may be utilized in an economical manner by their admixture
with coal or carbonaceous material, and bitumen, if required, and other substances,
as herein-after described.
30 tons of small coal as per analyses hereunder Al.

page_text: Thirty tons of coal highly bituminous, and 20 tons of anthracite coal have been
taken to shew that even coal can be selected to produce a specific result, as well as
the other substances mentioned.
The manganese in the mixture will assist in removing the sulphur contained
therein.
The components of Al, A, H, and K, will all assist to make a coke and supply
the carbon. Many of the ingredients will assist to form a good slag. The combi-
nations of thevarious substances to be used for producing the metallic compound to be
smelted will depend on the results required.
Having pulverised, mixed, and coked these substances in the manner herein-before
stated, and calculating the loss in coking to be :-
In Coal 30%
Pitch
=
=
15 tons.
16°
33
3
"
Iron peroxide 10%, reduced to protoxide
=
4.6
"
37
Peat 50°
=
20
37
"
3
Palomare's ore 6°
Limestone and clay 50%..
extra
-
-
5
"
=
0.9
"
The result would be 138 tons containing about :—
Protoxide of iron
2
Do.
Carbon
Silica -
Alumina
Lime
-
Magnesia
manganese
Potash and ash
Sulphur
Phosphorus
37.2 %
=
1.7 "
40.0
"
10.4
"
3.7
"
3.6
"
0.1
"
=
3.3
33
100.0
This when smelted with iron ores, or without ordinary coke, will produce pig iron.
The above proportions of materials are not arbitarily fixed, nor is it suggested that
they should be all employed to form the compound, the foregoing example being an
extreme case, given for the purpose of showing that a careful study of the analyses
of various substances will enable the operator to use and blend them advantageously
one with the other, both as regards quantities, qualities, and cost.

page_text: The ingredients should be varied according to the different characters and
analyses of the metalliferous and other substances to be smelted with the metallic
coke, the object of mixing the various substances being of course to enable the
smelting to be effected with ease and facility.
If the coking is not done prior to the introduction of the mixture into the blast
furnace it will be necessary to form it into lumps or bricks which will hold together
while coking in the furnace.
I am cognizant of the fact that several attempts have been made to deal with
ferreous substances in powder by mixing them with coal and even bitumen, and
coking them or making them into blocks, but these have never been brought to a
successful issue, because, the intention having been to smelt the mixture alone, it
was considered important to produce coke or blocks containing the largest possible
per-centage of metal, as compared with the per-centage of carbon, or that the carbon
contained in the coke should not be in excess of the quantity required for the
reduction of the metallic oxides also contained therein; the resulting product was
therefore unfit for use in a blast furnace, and the attempts to carry on the process
have been abandoned.
As the pitch or other bituminous matter is added principally for the purpose of
making the coke or blocks sound, the quantity used (if any) must depend on the
quantity of coal or other carboniferous materials used.
I have ascertained that in order to make sound metallic coke it is necessary
that it should contain an excess of carbon beyond what is required to smelt the
metalliferous substances in the mixture, and to smelt it economically, additional
metalliferous substances must be smelted therewith, in order to utilise this excess.
This can be done by the aid of an additional quantity of metalliferous and fluxing
materials, with or without the addition of ordinary coke.
When utilizing and smelting substances of small value the economy of carbon is
of vital importance, whereas when producing specific alloys or smelting substances
difficult of reduction it may be advisable to employ the excess of carbon, in order
to facilitate the reduction of the metalliferous substances. This process is par-
ticularly adapted for the production of metallic compounds or alloys, such as
ferro-chromium and iron alloyed with chromium and manganese, as in the examples
given, or iron alloyed with titanium, tungsten, nickel, or other metals, as the
relative proportions of metals and other ingredients in the mixture can be very
easily controlled, thus enabling the operator to produce specific quantities of metals
and of metallic alloys, and other desired combinations thereof.
In addition to these advantages the intimate and close admixture of the metal-
liferous with the carboniferous and other substances facilitates the smelting, especially
in the case of metallic oxides, which are difficult of reduction.
Further, the ingredients being in the pulverulent state, objectionable constituents
can be more easily removed by washing or other purifying processes; for example,
ores containing phosphorus after being pulverised can be washed, to get rid of the
fossil remains which are found in aqueous iron ore deposits, and these, as well as
other iron ores can, if desired, be treated with sulphurus or other acids, for the
purpose of further reducing the per-centage of phosphorus, in order to render it
suitable for the manufacture of the better qualities of iron and steel. This
pulverulent condition of metalliferous substances has heretofore been considered a
serious difficulty, especially when it has been attempted to smelt a large proportion
thereof, as compared with the remainder of the burthen in the blast furnace; in
order to overcome this many processes have been devised. In my process, however,
this condition is an advantage, if not even a necessity.
When non-coking coal or other carbonaceous material is used, or metalliferous
substances which are reducible at a temprature which renders coking only partially
or altogether unnecessary, it will be advisable to mix the ingredients together, in a
heated state preferred, and form them into blocks by pressure, taking care to use
sufficient binding materials, say, for example bitumen, in order that the blocks may

page_text: hold together. These blocks may be baked and partially or wholly coked before
introduction into the furnace, and if not wholly coked the coking and smelting will
be completed in the furnace.
It will be understood that the reason why I have not definitely described the
quantities of the various ingredients proposed to be mixed in the production of the
metalliferous compounds is owing to the fact that the ingredients to be treated vary
so much in their components; for example, metalliferous substances, the fluxes and
even ores from the same mine, are found to differ considerably in their components,
and the same remark also applies to coal and other carboniferous substances, there-
fore the proportions of such ingredients must be regulated by their composition and
bituminous qualities, and by the analyses of the metalliferous and other substances
intended to be used with the metallic coke, as will be well understood by persons
experienced in smelting metals.
may mention as some of the advantages of my process,-
Firstly. The disintegration of the various materials employed; (a) renders it
possible to remove objectionable matter by washing or other means; (b) renders the
reduction more facile, owing to the particles of oxides or metalliferous substances
being brought into direct contact with carbon, and the silica being also brought
into similar direct contact with carbon, and if desired with the bases necessary for
fusion; hence a smaller quantity of metal is lost in the slag when dealing with ores
such as manganese, the protoxide of which has a great affinity for silica.
Secondly. The various substances can be arranged in the mixture so that any
deficiency or excess of any of the constituents can be compensated.
Thirdly. Many oxides, such as those of chromium, titanium, cerium, manganese,
and others, resist the action of carbonic oxide at even a high temperature, and are
yet reducible by intimate contact with carbon or with metallic iron and carbon.
Fourthly. In coking the mixture a chemical action takes place and the particles
are brought into very close contact with each other; the mixture is swollen by the
heat, and the hydrocarbons evolved pass through the mass, and thus part of their
carbon is brought into close and direct contact with the oxides, thus materially
assisting their after reduction.
Fifthly. Economy in consumption of carbon.-A much larger proportion of carbon
is used in the reduction of oxides than is theoretically necessary.
The following are some of the reasons for the economy of my process,-
(a.) The iron in the metallic coke being principally in a state of protoxide
requires less carbon for the purpose of reduction than it would if in the form of
peroxide, whereas iron ores containing protoxide of iron are not easily smelted. It is
probable that protoxide of iron is not reducible by the direct action of carbonic
oxide, and that its reduction in the ordinary blast furnace is due to the carbon
which is deposited by carbonic oxide becoming split up into carbon and carbonic
acid.
(b.) The oxides in the coke being reduced by direct contact with carbon, the
reduction would probably be effected almost with the theoretical amount of carbon
necessary.
(c.) The excess of carbon in the coke will assist in the reduction of the additional
ores added to the charge of metallic coke, and the oxygen from the oxides in the
coke combining of necessity with the carbon will serve for the same purpose.
I therefore claim as new and of my Invention, the utilization of metalliferous
substances difficult of reduction by ordinary methods, and the production of ferro-
chromium and other specific qualities of metals or metallic alloys by the manufacture
of metalliferous compounds, in which the metalliferous and other substances (from
which, when desired, objectionable ingredients have been removed) are selected and
mixed in the proportions necessary to produce, when smelted alone or with other
ubstances, specific metals or metallic alloys, and other desired combinations thereof,
he carbonaceous materials being used in quantities large enough to produce a sound
coke or block capable of being smelted alone if desired, or with other metalliferous
ubstances, to utilize the excess of carbon beyond the quantity required for smelting

page_text: the metalliferous substances contained in the metalliferous compound, and with or
without ordinary coke, all substantially as herein described.
In witness whereof, I, the said John Hollway, have hereunto set my hand and
seal, this Nineteenth day of July, in the year of our Lord One thousand
: hundred and seventy-seven
Witness to the signature,
THOMAS WRIGLEY,
75, Chancery Lane, W.C.,
London.
JOHN HOLLWAY. (L.S.)