F. A. EUSTIS,‘ C. R. HAYWARD, H. M. SCHLEICHER, AND D. BELCHER.
ART OF MAKINGAELECTROLYTIC IRON.
APPLICATION FILED JAN. 17, 1922.
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Patented Oct. 17,1922.
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FREDERICV A. E'U'STIS, OF MILTON, CABLE R. HAYWARD, 01E‘ QUINCY, AND HENRY 1h
SCHIIEICHER AND DONALD BELCHER, OF BOSTON, MASSACHUSETTS, ASSIGNORS,
> BY DIRECT AND MESN'E ASSIGNMENTS, OFONE-HALF T0 SAID EUSTIS AND ONE
HALE T0 CHARLES‘ PAGE PEBIN, OF NEW YORK, N.. Y. A
AM‘ or MAKING nrncrnorxrrro mom.
Original applicationp?led December 1, 1920, Serial No. 427,541. Divided and this application ?led Jan
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nary 17, 1922.
- To all
it may concern .'
Serial No. 529,859.
ing the subject-matter. of the present appli
-
Be it known that we, FREDERIC A. EUSTIS, cation has to do primarily with the use of
of Milton, CABLE R. HAYWARD, of Qunicy, ferric oxide as the source of iron ‘and we
both in, the county of Norfolk, HENRY M. will therefore describe‘ herein only such fea 55
5 SoHLmoHER and DONALD BELOHER, of Bos tures‘of the general process as are necessary
ton, in the count of Suffolk, all in the to make clear its applicability to the treat
Commonwealth of if assachusetts, all citizens ' ment. of oxides of non. The oxide of iron
of the United States, have invented new and used as the source of iron in the present
useful Improvements in the Art of Making process is preferably in the form of an OK
10 Electrolytic Iron, of which the following is idized ore _of iron such as limonite7 hematite
a speci?cation.
60
or magnetite.
- '1
TheY ferrous solution from which iron is
of electrolytic iron from solutions,'and par deposited by electrolysis may be a solution
ticularly to the preparation of the ferrous of ferrous chloride in water, a ferrous sul
This invention relates to the manufacture
15 solution from oxides of iron for the elec
trolytic deposit of iron.
65
phate solution, or indeed a solution contain
ing any salts of iron that will in solution
The present application is a division of an dissociate to deposit iron under the action
application ?led by us December 1, 1920, of electrolysis, that will form the two series
Serial No. 427,541. now Letters Patent of of salts, ferric and ferrous, and that will at
70
20 the United States No. 1,412,174, dated April tack the ore or other raw material constitut
11,1922, and is addressed particularly to that ing the source of iron.
The ferrous solution when made by the
modi?cation- of the invention described in
our said former application adapted for the method hereinafter described will contain
treatment of 'oxidized ores of iron, or other at least some acid or ferric salts, such as 75
25 oxides of iron.
‘
ferric chloride,~ although it may be only
It has heretofore been considered that traces, and must be thorougly neutralized
oxides of iro? were‘ practically insoluble, and before it is suitable. for the production of
so far as we are aware they are insoluble electrolytic iron’, because the presence of acid
by any process heretofore known. Therefore or ferric salts causes a poor iron deposit and 80
30 oxidized ores of iron, and other sources of results in low current efficiency‘. To this end
ferric oxide, have not been considered prac the solution is mixed with pulverized lime
ticable sources of supply for the manufac stone in a suitable tank. Limestone furnishes
ture of electrolytic iron by dissolving iron calcium carbonate (CaCO3) which is the
to form a ferrous solution and thereafter most suitable agent for neutralization, as it 85
85 depositing iron from the solution'by the ac 'has the capacity of readily precipitating
?rst ferric salts before precipitating the fer
tion of electrolysis.'
>
We have discovered that oxides of iron rous salts. We have found that for the best
may be dissovled from oxidized ores of iron results it is advisable to use enough neutral
or other similar source by means of a sol izing agent to precipitate a small amount of 90'
40 vent containing dilute acid and suitable ferrous iron. This insures complete neutral
quantities of ferrous salts. For example a ization of the liquor, the neutrality of the
solution containing dilute hydrochloric acid solution in the cathode compartment of the
and a generous quantity of ferrous chloride, electrolytic cell being an indis ensible con
or a solution containlng dilute sulphuric dition for the most 'e?icient e ectrolysis of 95
45> acid and a generous quantity of ferrous sul
The solution is then ?ltered if necessary,
phate, will act as a solvent of oxides of iron
and after reduction form a ferrous solution heated nearly to the boiling point, and
. suitablefor the electrolytic deposit of iron.‘ passed hot into the cathode com artment of
For a detailed description of our processv a diaphragm electrolytic cell. Uiider proper 100
to as a whole reference is made to our said conditions metallic iron is deposited on the
iron.
A
I
Patent No. 1,412,174. The invention form? cathode. , The liquor passes through the dia—
Q.
1,482,54M
phragm into the anode compartment and is _ pects the procedure may be the same as
thence returned to the process to be used indicated in Fig. 1.
in ‘making more ferrous‘ solution as herein
The reason for returning the greater part‘
after described.
of the liquor from the ore solution tank to
A special electrolysis cell A is used for the reducing tower or the reducing cell as
depositing the iron, of theqkind fully de- the
case may be, is that the e?’ect of the
scribed in our said former patent to which action of the leach liquor on most oxidized
reference is made for a more detailed de ores isto take some of its iron into solution '
10
15
scription of its construction and mode of. in ferric state; therefore, the solution com
from the ore solution tank will contain
The accompanying drawings indicate dia~ ‘ing
ferric salts and must again be reduced.
grammatically apparatus for performing the If all the liquor were sent direct to the
process, illustrating in two alternative forms vlimestone neutralizing tank it would be
the cycles of operations.
necessary to use large amounts of limestone
operation.
‘
‘
.
I
Referring ?rst to Fig. 1, thevanode‘ liquor for . neutralization because of the large
containing ferric chloride and ferrous chlo amount
of ferric chloride present in the so
ride, (or ferric and ferrous sulphates if the lution dissolved from the ore. This is not
80
original solution was a sulphate instead of only costly in limestone but may-use up too
a chloride) should ?rst be reduced to a
20 ferrous solution. The hot anode liquor is much acid in the neutralization step. There
fore, a part of the solution is sent from the 85
discharged from the anode compartment of ore
solution tank back to the reducing cell
electroiytic cell A into the top of a reducing where the ferric chloride dissolved from the
tower packed with coke. A gas contain ores is‘ reduced, and the solution so reduced
ing sulphur dioxide (S02) is introduced at upon
again passing over the ore picks up
25 the bottom of the tower and rising through
more ferric iron but only one-third as much
the tower comes into contact with the de as was present immediately before it was
scending solution. This reduces the ferric reduced. Thus by repeatedly cycling part
chloride (or sulphate) to ferrous chloride
' (or sulphate) and the resulting liquor dis of the solution through the reducing tower
30 charged from the reducing tower contains and over the ore the ferric iron in that .part
of the solution advanced "to the‘ limestone
a large amount of ferrous chloride (or sul tank
may be diminished tov any point de
sired.
35
C5
phate), a small amount of sulphuric acid
and a small amount of hydrochloric acid. / Since sulphur dioxide is not used- for
This constitutes a leach liquor by which the reduction
in the procedure indicated in Fig.v
oxides of iron may be dissolved from the 2, but merely electrical
energy, there is no 100
oxidized ore. This liquor possesses a pecul source of new acid in the.
cyclic process it
iar ability with great rapidity and sub
stantial completeness to dissolve the rela self and the acid must therefore be carefully
‘
>
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conserved. This Ncan be done by turning a
tively insoluble ferric oxides. The reduced large
portion of the solution from the ore
leach liquor is then put on the ore in a
solution tank B where it dissolves iron from
the ore, and is then ?ltered at C. Thence
the major part of the solution is pumped
solution tank back to the reducing cell and
advancing only a small portion to the lime
stone tank for neutralizing. Even with this
mode there is some loss of acid which can
. back to the top of the reducing tower, while economically bev restored by blowing S02
'45 the smaller part will be advanced to lime gas
into the liquor in the reducing cell or
‘stone tower D for neutralizing and there-'
after electrolyzing at A as before. The part
which is sent to the limestone tower may
optionally .be passed through scrap iron in
a tank F for the purpose of further enrich
ing the solution in iron and at the same
tlme using up part of the acid coming from
105
at some other convenient point.
-
-
110
When the reduction of the anode liquor is
performed by an electrolytic reducing cell,
oxygen comes off at the anode of’the reduc
ing cell during the electrolysis if a sulphate
electrolyte is used, and may be'recovered as
115
a by-product. When a chloride electrolyte
is
used chlorine gas is given off and for this
As an alternative method of reducing the
55 anode liquor, it may be delivered ‘from the reason the electrolytic method of reduction
is less desirable for chloride solutions than 120
main electrolysis tank A in which the irony fon
sulphate solutions.
"
.
is deposited, into a second electrolytic cell
The
ore
to
be
treated
in
the
solution
tank
G (see Fig. 2) which may be termed an elec B should be ?nely ground or pulverized to- trolytic reducing cell. The application of insure
an efficient and speedy action of the
60 electric energy to the ferric solution in the
solvent.
Many oxide ores occur in nature
electrolytic reducing cell G ‘will reduce the
solution from the ferric to ferrous state. in ?ne condition and such will require only 1,25v
This reduction of the ferric salts formed in a ?nal pulverizing treatment. The mixture
the solution tank should be maintained
the electrolysis cell A furnishes acid needed in
at
a
high temperature, as the hotter the mix
for dissolving the oxidized ore. _ In QthQI’ 1'6"
the solution tank B.
‘
ture the more e?’ective is the action. Good 130
naeaeee
results may be obtained at a temperature of
70° C. and above. It is also desirable to
stir or agitate the mixture in order to insure
constant contact of active solvent with the
ore; or percolation may be used. A counter
6. The art of making electrolytic iron
which comprises reducing a. solution con-1
taining ferric salts by means adapted to pro-. \
duce a solvent of oxides of iron consisting of 50
a solution containing ferrous salts and dilute
curr'ent method of leaching is advised, by acid, dissolving oxide of iron in said solvent,
which fresh ore is treated with the weakest and _ depositing iron from said solvent by
solution and the residue of the ore is treated electrolysis.
with fresh solution.
_ C
7. The art ofv making a ferrous solution,
,
55
It will be understood as already indicated suitable for the electrolytic deposit of iron,
15
that the procedure is essentially the same which comprises reducing a ferric sulphate '
whether- the ‘solutions used are chloride or solution by means adapted to produce a sol
vent of oxides of iron consisting of a solu
sulphate solutions.
tion containing dilute sulphuric. acid and 60
‘We claim:
1. The art of makin a ferrous solution, ferrous sulphate and dissolving oxide of
suitable for the electrogytic deposit of iron,
iron in said solvent.
,
8. The art of making electrolytic iron
which comprises the step of dissolving oxide
of iron in a solvent containing dilute acid which comprises reducing a solution con
taining ferric salts by means adapted to pro 65
.
duce a solvent of oxides of iron consisting
2.
The
art
of
making
a
ferrous
solution,
20
of
a solution containing ferrous salts and
suitable for the electrolytic deposit of iron,
.‘ which comprises reduclng a solution con dilute acid, dissolving oxide of iron in said
taining ferric salts to produce a solvent of solvent, depositing iron from said solvent by
oxides of iron, and dissolving'oxide of iron electrolysis leaving a ferric solution suitable 70
for reduction according to the ?rst :Step
'
25 in said solvent.
3. The art of making a ferrous solution, hereinbefore speci?ed in order to be again
suitable" for the electrolytic deposit of iron, made into a solvent, thus completing the
and a ferrous salt.
which comprises reduclng a solution con
cycle.
9. The art of making electrolytic iron
taining ferric salts‘ by means adapted to pro
which
comprises reducing a solution con
30 duce a solvent of oxides of iron consisting
of a solution containing ferrous salts and taining ferric salts by means adapted to
dilute acid, and dissolving oxide of iron in produce a solvent of oxides .of iron consist
ing of a solution containing dilute acid and
said solvent.
4.,The art of making a ferrous solution, a ferrous salt,‘ dissolving 1ron in said sol
35 suitable for the electrolytic deposit of iron, vent, dividing the resultant iron solution so
, which comprises reducing a solution con formed, returning part thereof to the ferric
taining ferric salts by means of sulphur solution at the reducing step for repeated
reduction, and advancing part only thereof
consisting of a solution containing ferrous for the deposition of iron by electrolysis.
dioxide to form a solvent of oxides of iron
40
salts and dilute sulphuric acid, and dissolv
ing oxide of iron in said solvent.
_5. The art of making a ferrous solution,
suitable for the electrolytic deposit of iron, I
which comprises the step of dissolving oxide
45
of iron 1n a solvent containing dilute sul
phuric acid and ferrous sulphate.
Signed by us this 9th day of January,
1922.
w
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‘
FREDERTG A. EUSTIS.
.
CABLE R. HAYWARD.
'
HENRY M. SCHL‘ETCHER.
DONALD BELCHER.
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