L. F. VOGT.
METALLURGICAL PROCESS.
APPLIOATION FILED JULY 21, 1913,
1,129,029. ’
Patented Feb.16,1915.
LOUIS F. VOGT, OF WASHINGTON, PENNSYLVANIA,- ASSIGNOR T0 STANDARD ('JHIE‘JMIÍICÉALl
'
COMPANY, OF PITTSBURGH, PENNSYLVANIA.
lltlIETALLU'RGICAL> PROCESS. '
1,129,029.
Speciñcation of Letters lt’atent.-
, Patented Feb. i6, 1915'.
Application filed July 21, 1913. Serial No. 780,339.
To all lwhom ¿t may concern:
prevent theexistence of radium or barium ‘
Be it known that I, Louis F. Voer, of in soluble form in the sodium vanadate
Washington, in the county of Washington lrquor (step C). After removing the sodium
and State of Pennsylvania, have invented vanadate liquor (which maybe stored for
certain new and useful Improvements in subsequent treatment), the solid material or - 60
Metallurgical Processes; and I do hereby' sludge, will be leached with mineral acid,
declare the following to be a full, clear, and preferably sulfuric acid, to recover the
exact description of the invention, such as uranium and suchvanadium as may, remain
will enable others skilled in the art to which lin the material, in‘solution. » If an acid other
than sulfuric be used, suílicient sulfuric acid 65
it appertains to make anduse the same.
This invention _relates to an improved should be` added to form an insoluble radium
metallurgical process for the extraction and sulfate and thus prevent any radium con“`
recovery of valuable constituents of ores and tent'ofthe‘sludge from going vinto suÍìutio‘ir.l
(step D). The sludge resulting from this '
more particularly to the extraction and re
covery of radium, uranium and vanadium step of the process will -comprise insoluble 70
radium and barium salts and.l the4~ liquor
15
Afrom ores such as carnotite ores,-one object
of the invention being to so treat ore con
will consist of u?anyl and vanadyl salts and
taining radium, uranium and vanadium as impurities, in solution.>
After separation' of the liquor from the
sludge, said liquor will be neutralized with
A further object is to provide a process suíiicient sodium carbonate to precipitate im#
for the treatment of -radium-bearing ore,- purities such as iron, alumina, silica, etc.,
which shall be operative with commercial together with a large portion of the uranium
'-to recover these constituents in maximum
20
quantities.
success to recover a maximum quantity of
25
the radium content.4
75
and vanadium. If'the solution contains im
purities in sufliciently large quantity, all of
80
. `A further object is to provide a simple the uranium and vanadium content would
and economical process for treating ore to be precipitated.
separately recover valuable constituents,
To the mixture (the solution and'precipi
such as radium, uranium and vanadium, or tate) resulting from the neutralizing step-
so any one or more of such constituents.
above described, an excess of sodium car 85
A further object is to so treat complex bonate will be added, and the mixture will
ore containing radium, as to separate from be boiled, the purpose of this step being to
the radium content, the other valuable con leach out the uranium and vanadium con
stituents of the ore,>step-by-step, leaving the tained in the precipitate, leaving the impuri
35 radium as the final product. .
ties in the precipitate (step A D1).
The
90
With these and other objects in View, the uranium and vanadium will now be in solu
invention consists in certain novel steps in tion as sodium compounds of these elements.
. the treatment of ores as hereinafter set forth
and pointed out in the claims.
40
4 The accompanying drawing is a diagram
This solution or -liquor-will then be sepa~
_rated from the precipitate by filtering or
otherwise, and will be treated to recover the
95
matical illustration of my improved process. uranium and vanadium, as follows: The. so
The ore (such for example as carnotite
lution of lsodium compounds of uranium
ore) will preferably be first concentrated in 4and vanadium is treated in a suitable tank
any approved manner or it may be merely
45
comminuted (step A).
concentrate or ore- will'
with a salt of lead,-such, for example as
The pulverulent lead sulfate or carbonate, the whole being
then be roasted in agitated and boiled with steam (step D2).
100
the presence of sodium chlorid and steam The lead salt will react with the vanadium
(step B), the latter being employed for contained in the liquor and form insoluble
oxidizing purposes. The roasted ore lwill lead vanadate, while the uranium will re
50 next be leached with water to remove the main in solution. The lead vanadate will 105
greater part of the vanadium content. To then be separated from the precipitate or
the water used in this step of the process, a sludge by filtration, decantation or other
small amount of sodium ‘carbonate will be wise, and the uranium solution (sodium
added to convert any possjrle radium or uranyl carbonate) which is now free from
55 barium chlorid to the carbonate form and vanadium will be treated for the recovery
2
1,129,029
of the uranium, as follows: The sodium sulfates ofradium and barium will then be
uranyl carbonate solution will be boiled separated in any suitable manner from the
' with steam or otherwise and sufficient sodi
um hydrate will be added to completely pre
refuse liquor containing the impurities, and
then dried. The dried sulfates of radium
and barium, which _are now of relatively
(step D3). This precipitate will be sepa high radium and barium content, will now 70
rated from the solution and then Washed and be thoroughly mixed with comminuted coke
dried, ready for commercial use.
or other suitable carbonaceous material and
The lead vanadate resulting from the lead a suitable chlorid (for example, calcium
l0 treatment 'above described may be boiled i_n chlorid), and roasted (step H). During
75
sulfuric acid to .leach out the vanadium the roasting, the sulfates of radium and
leaving the lead in the form of lead sulfate barium are converted 4to chlorids. The
which may be used again for removing roasted mixture will then be leached with
vanadium from the uranium- vanadium so .water to dissolve the chlorids (step I), leav~
cipitate the uranium as sodium uranate
lutions hereinbefore described.
-
The solid matter or sludge, referred to as
resulting from step D, and comprising in
soluble radium and barium salts and im
20
25
30
,..
ing insoluble, the remaining carbonaceous
80
material, which latter will be filtered ofi",
leaving the radium and barium chlorids in
the liquor.
The radium may now be sep
purities, will be Washed, filtered and dried. arated from the barium and impurities
The dry material will ythen be thoroughly
systematic fractional crystallization
mixed with sufficient sodium carbonate to (step J).
flux the mixture whenheated in a furnace.
It will be observed that during the per
The mixture is then subjected to sufficient manence
of my improved process, the ura
heat (approximately 2200 F.) in‘a suitable nium, vanadium,
and other constituents of
furnace, to fuse the mixture and render the the ore are separated,
step-by-step from the
same Huid, (step lE).A During this fusing` radium
content
of
the
ore, always holding
step, the following reactions have taken back or leaving the radium
insolu
place: Silica has largely become sodium sili ble, until the final separationcontent
of >the radium
85
90
cate, and the radium, barium, lime, iron, from the barium is accomplished by sys- `
etc., have become their respective carbonates. tematic
fractional crystallization.
95A
The iiuid material, upon being discharged
Having fully described my invention
35
40
45
from the furnace, will be spread out in a
suitable manner to permit it to cool in the what I claim as new and desire to secure by
Letters-Patent, is :--'
form of thin Hakes (step E).
The herein described method of reduc
The cooled and flaked matte, consisting> ing1. carnotite
for the recovery of the 100
of carbonates of radium, barium, iron, lime, radium content,oreconsisting
in roasting the
etc., together with sodium silicate and ex
ore
in
the
presence
of
sodium
chlorid and
cess of sodium carbonate, will be treated
with water and agitated in a suitable con~ subsequently subjecting the material to suc- ‘
treatments to remove the vanadium
tainer, so that the sodium silicate contained cessive
and then the uranium compounds, leaving 105
in the material will be dissolved, leaving
radium and barium as insoluble com
the insoluble carbonates suspended in the the
pounds,4
then converting said radium and
liquor (step F). These insoluble carbonates barium compounds
to av soluble state in `
will then be separated from the liquor con
solution,
and
finally
subjecting
the solution
taining sodium silicate, by filtration or of barium and radium compounds
to sys 11o
otherwise, so that the carbonates may be re tematic fractional crystallization and
re
covered freed from a large portion of the covering radium salt free from other com
silica which the material contained. The pounds as a final product.
carbonates will then be washed with water
remaining sodium silicate
The said carbonates will
then be comminuted in any suitable manner
and mixed in water, thus making an aqueous
mixture in which the comminuted carbon
55 ates are held in suspension. The aqueous
mixture of carbonates is introduced into a
50 to remove' any
u and free alkali.
60
65
~ 2. The herein described process of treat
ing ore containing vanadium, uranium and
radium, for the successive .elimination of
115
vanadium and uranium and the final re
covery of a salt of radium, consisting in
roasting the ore in the presence of sodium
chlorid and an oxidizing agent, leaching
the roasted.- Amaterial and 'obtaining a solu
suitable tank containing mineral acid, pref tion of sodium vanadate, _separating the
erably hydrochloric, in quantity suiiicient solution
from the sludge, leaching said
to dissolve the carbonates completely, leav
ing a slight excess of free acid (step G). sludge with a solution of sulfuric acid-and
By now adding sulfuric acid to this solu obtaining uranyl and vanadyl'lsalts in solu
tion, separating the solution from this
tion, radium and barium sulfates are pre sludge,
subjecting the last-mentioned
cipitated and remain insoluble, (step G1), sludge tothen
treatment
for the elimination of
while the impurities (such as iron, alumi
num and lime) remain in solution. The the constituent materials from the radium
content, treating said radium content to
120
1
125
130
1,129,029
render the same as a soluble radium salt,
3
sulfates with -carbonaceous materia] and a
and finally recovering said soluble radium chlorid; leaching the roasted mixture and
salt free from other compounds.
3. The herein described process, consist
recovering chlorids of radium and barium
in solution; and then subjecting said solu
ing in fusing radium bearing material with tion of ‘adium and barium chlorids to sys
an alkali carbonate; then leaching with Wa tematic fractional crystallization to remove
ter; then dissolving the resultant radium the barium and krecover radium chlorid.
carbonate in acid; adding sulfuric acid, and
6. The herein described process consist
recovering radium sulfate.
ing in roasting ore containing radium, ura
4. The h lein described process, consist
nium and vanadium inthe presence of so 35
ing in fusinì radium bearing material with dium chlorid and an oxidizing agent; leach
15
an alkalil carbonate; then leaching With'wa
ter; then dissolving the resultant radium
carbonate in acid; adding sulfuric acid, re
covering radium sulfate; roasting the ra
ing the roasted material and obtaining a
solution of sodium vanadate free from ra.
dium; leaching the resultant sludge with
_fluid containing sulfuric acid and obtain
dium sulfate with carbonaceousmaterial and ing a solution of uranium and vanadium
a chlorid, leaching the roasted mixture and' and free from radium; then treatmg the
recovering radium chlorid in solution.
' resultant sludge for recovery of radium.
5. The herein described process consist
In testimony whereof, I have signed this
ing in fusing material containing radium specliicatlon 1n the presence of two sub
and barium, with an alkali carbonate; then scribing witnesses.
leaching with Water; then dissolving the
LOUIS 1". V(.)G'l`.
resultant radium and barium carbonates in
acid; then adding sulfuric acid; recovering
R. S. FERGUSON,
radium and barium sulfates; roasting said
S. C. HILL.
,
25
Witnesses:
y
.
40