Патент USA US2606151

Aug- 5, 1952
M. J. PORTANOVA ET AL
2,606,143
PROCESS FOR ELECTROLYTIC PREPARATION OF VANADIUM OXIDE
Filed Nov. 2, 1948
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42.
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34
_
l5
38
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39
INVENTORS
'
M01710 J Portanova
ATTORNEY
'
2,606,148
Patented Aug. 5, 1952
PATENT‘
_ ritoonss FOR; ELECTROLYTIC PREPABZA-. ',
j'TlQNOF VANADIUM OXIDE '
.: MarioJrPoItanova; Brooklyn,
7
Y., and Arthur
Rcsinger, Belleville, N. J ., assignors to Natural
Products Re?ning 00., Jersey City, 7N.‘ J.,‘ a.
corporation ofDelaware
» Application November
' p
a
2, 1943; ‘Serial 'No.‘ 57,864
1 43 ‘Claims. (01.204-96)
;; sulfuric acid ‘ containing ‘23% by, Weight ofivv'ater,
--tov_precipitate out the crude sodium polyvanadate.
:Qerinvention :Ielates, to theprqcess .0f.~:preparr
wing:vanadium"OndeQYZzOebY the; electrolysis of
The sodium polyvanadate is usually: a - mixture
Sodium vanadate; NaVoai solutionsrandzthe ap
_-_ of~variab1e proportions 'ofithe following acids,‘
aearat?s. usedtherein
.‘e'nufacture of, whisk-purity yanadiumaexida
5
wpyartly dehydrated; with'the sodium salts there
i-jyof:
v vJand anothereobject is to providerian velectrolytic
-
1
Orthovanadic acid, OV(OH)3
6.911; for enablins..ihe.:process to‘ becarried; out
'Metavanadic acid” VQzKOH) ‘
‘ all-effective and. medicalswam-than. aren “.10
and ofttimes, also; onefor‘both of'jthe .following
In the practice of thisfinventionathesodium
. acids, partly dehydrated, 'withfthefsodium ‘salts
r-lo-meialwanadete
-
~
.
.
~
.
vxanadete solution used: for:§1ectro1ysis_;may be
thereof ':
"remained "in: any: desired l'way- Q Fpriexain-ulerthe
fvisaidvanadate solutionl maybe produced by leach
» g-eutvtbeieavstmade by heating orjfusmeunder
xlwizirlgrcsinditious any vanedium:.hearing~;ma
Tetravanadic v“acid,
Y
, vororn z.oyoonovoorrovorom 2
Previous electrolytic-7 methodsl' of! treating ‘ “the
wisriel 01' 1 0m- with- one ~ or‘. more? alkali. metal
compounds such; fprizinstarmesesisedimen
benete, -,sQ.d1ium~hY.d¥9X,-.ide,1 pqtetsium carbonate,
.> sodium vanadate lsolutionslto produce ‘ vanadium
oxide resulted in obtaining a1 ‘vanadium? oxide
containing considerable" amounts of sodium jjcom
wpounds and other ‘impurities-such‘ asdlinier and
20
.-..imjte~s_,si.u_m.- .hyereaisievor ~ mixture s thereof 1 in any
,
.v_
‘ I desiremrproportions.
.~_Another» a
..
, ‘ Pyrovanadic ‘acidL vorori) 2,0310; (em
.
and; obtaining
1' J silica; ‘ and; furthermore,“ the {use} of anodes" of
> the sQdium-Yvanadate solutionimayibe by: diesel‘!
’goxidizedrvstater-in> aqueous-.; solutions ‘of alkali
p1a'tinum,1€whi'ch has‘ previously been said‘to, be
theionly metal ‘that-Willi'resist ‘the electrolytic
1?iiimkiartonate,.pqtassiilm-ihydroxidei potassium
,methods impracticaljand too expensive. -
1 111g:ahykvaileqiumrbearinematerial or" vore Linen
oxidation’ at that anode-has 'made the previous
imétalwqofripoueds Such as sodiumhydrox'ida s0
An ‘object of our invention, thereforegis'to
provide an electrolytic'cell by means of'iwhich
wear-bonatefor mixtures, thereof, in any-desired
~ proportions. ~ These methods of- obtaining theso
,.Ivi_ously.,wellglrnown. v Forrexamplea-vre canrpre
the process above referred to c'anbe e?ec'ti'vely
accomplished and inv which anodes and-cathodes
of an: effective "character, made of-readilyl avail
",parei a sodium vanadaterlsolutioni?rom a vana
able materials-‘areutilized, anduin- which, by
s ; dissolved; in ‘- caustic: soda‘ solution 15 or ‘mother
lialk?lliéi?etal ‘iompqunds. " 7 solution- ?uehtreat
the Y concentrations, temperatures} and ~ current
',
or otheuv alkali-vmetalf vanadate;vv solutions
.flm‘ irieatmsntbyblirPuws are pi-wmise-v-snre
30
means of a rotating ‘anode the vanadium-oxide
v._di1'i__rnV-.b,eairing ,material such7 as: a; crude-riserdium
may be e?ectively removed continuously in the
- .polyvanadate; obtained as, a ivy-product nirvan
u‘sjindufstriesfflfhis impure sodium .polyvanadate _ ~process 1byscraping the precipitated vanadium
oxide therefrom.
densities in the process'to enableiitheseadvan
“ment ‘of’ at crudev sodium rpolyvanadatef ore; other
'tageous objects tobeattained; '
impure vanadiumébearing “material .;-in » the 1 ; ox
Qidized state? has ,the. advantage -that;~_;any_ ‘m
..40
Tpuritiesg-insoluble in; alkaline\} solutions an the
‘spare-ted immthe Soluble; sodiumwanedeterby
a-?ltration or. settling, before v'elec rolysis.
Another‘ object is to control
'
“
\‘While our invention ‘is capable5of1being‘ car
ried out in many different-ways and withmany
di?erent' types of.» apparatus, by' way of- example
we have shown only. one embodiment'ofi-the ap
in- the . accompanying drawings,‘ ' in
' paratus
' The Yvcrude fsodium-polyvanadate referredito
45
may. for/instance; keel-that ftvhicl'iv is obtained; as V.
:Fig; l is .-a vertical'se‘ction of ‘an electrolytic
4a prqduct vinl the {woven . of ,.»11rani1-im _» 15.119!“
cell ‘usedinv accordance'with our‘ invention; and
mranium: oresf; for instance ‘- by‘ roasting; uranium
Fig. 2 is a plan view of 'the‘same.
‘
~éoIré~wntaining vanadium, compounds as anytim
--The present ‘process; by employing theHtype
-‘-purit-y,with~: an alkali-metal compound such: for
example, asvsqdium carbonate-stadium‘hydroxide, > 50' ofv apparatus‘ hereinafter ‘ described‘ together’ ‘with
which—
izgpotassium carbonate, potassium hydroxide or
e‘xnixtures ‘thereof in. any desired.‘ proportions; yto
irproducenan'_ alkali uranium compound_.;_ and then
1 treating the; product thus obtained with‘sulturic
. ,1 acid got:‘ any, desired strength, -,‘out for instance . '
,
‘
,
’
'
'
~
I
the conditions of proper concentrationand-sub
<sequent repulping'of the vanadium oxide, results
in‘the manufacture of, a high gradeproduct- con
taining even- as much as >97~%~>~vanadium~oxide,
‘,thezremainingg.-3 % being‘ substantially-‘comprised
9,666,148
3
4
bf sodium oxide. This product compares favor
any in composition with the best previously obe
tain'able ‘product of the highest available purity
on the market. one or the important features
fof ear hvéntibn, furthermore, is utilizing steel
inist‘ead ofplatinu-m'as the anode material, as
we hayediscover'ed that steel,- ‘c'ontra'ry-to pre
‘vious knowledge, will withstand eifectively the
rying a stationary brush l9 which is connected by
a wire 20 to the source of electric current to
which the wire [5 also leads. The said shaft I8
has securely fastened thereto a bearing member
2| having beneath the same a ball race 22 to re=
=ceive, balls 23 supported
a stationary ball race‘
» 24, to act'as a thrust'b‘earing for supporting the
shaft I8, by being carried within an insulating
‘corrosive ‘electrolytic attibn at the anode owing" > . .?bre clamping block 25 secured by screws 26 to
‘to the formation 6f
a protective v?lm ,of oxide .10v a yoke “21, the lower downwardly directed éiids
bf iron
The making "ofxthejianode of f "
of which are ?ancee and‘fastened by screws it!
‘steel
and silicon,
"or jiii‘bi’l, such
or of as
iron
cast'irori,
alloys containing
'etc.,~~mak'es
carbon
this"
to ?anges '29 located on the top or a horizontal
annular ‘cover plate 30‘ which connects thewalls
lprebess especially practical. and feasible for the ‘I "and 5, ‘forming the chamber 2 located between
Imanufacture of vanadium oxide commercially; 15 the‘
same. The porcelain cylindrical diaphragm
In fact, by this means any water soluble alkali‘; ‘
l i; furthermore, has on its inner face two vertical
and 311, respectively, for receiving therein‘ scrapers
metal vanadium compound maybe ‘eifectively
electrolyzed to t'ai‘od'llfie the vanadium oxide by,
our process,
?anges 3| and 32_ provided with vertical slots 33
\
As an example in carrying but the process, and
' 35 and 36, made of any desiredlinsulating inert
, _ means which may be ‘utilized in'c'ai'rying ‘out this
thereof the ‘against the rotating steel anoee Ii
to remove-‘the ‘vanadium oxide, which fofnls
?exible or plastic material so that the inner edges
inventionetne erucesodium' or potassium fpo1y=
, vanadate {maybe converted to a soluble sodium
vana'd'ate;\ by digesting‘ it
,_ or other alkali-metal
- taerepn during the, élect'iioly‘sis.
-
. ‘with aba'ustic' soda-‘solution or other alkali-metal 25
compound in aqueous solution; The said caustic
soda, solution or ‘other alkalhmetal compound
aqueous “solutionv
contain any desired oer=
centage erwater, but for instance‘frorn 1/27,, _to
nim?!”
' there is also a draweoff pipe‘ 38 having a valve
3'9 connected-to ‘a pipe {10 for carrying off the
discharged__ liquid; Furthermore, in the anode
‘chamber i6 there'is a supply pipe 4|... _‘ Thev cathe
‘Weight otwater. . ‘The solution is prefer; 30 ode chamber l3 maybe provided with an over
.
l,
.
.
.
: ably'hdju'sted to a .pH of 7.031331 using; a slight
new pipe 42, if desired.
excess of alkali polyvanadate; The insert-merm
* purities are then ?ltered off. The filtrate is then
setto a concentration
v _
of ‘.96 ea;_} of vanadium
,
oxide peer to. this gr}. Navo's' her to.) a; This se=
' lutioh is'new run intov'the anode chamber of a
twoecompartment cell, constructed‘ as hereinafter
described, Thecathode chamber is ?lled with a
. caustic soda solution which is preferably weak,_
I
'
A
__
l
- ‘In the operation of our process, the outlet
valves 9 and 39 of the cell being in closed posi
tion, the-cathode chamber I3 is ?lled with the
weak caustic soda solution comprising, prefer
j ably, a solution of 1% by Weight of sodium hy
droxide in water, by‘ means of the pipe 31. The
anode chamber'?i is then: ?lled, by means of
the
M, with the sodium vanadate solution,
‘haying _a,~1%~_strengti_l foninstance. ,
4 l
40‘ thatpipe
is to "say containing the crude sodium poly=
a v ., The;two-compartment;;electrolytic ce1l-is,;for
"vanadate obtained as above and having the
. bxampl'e, provided with-anv outer hollow cylindri
" strength above referred to, as for‘ instance a corl=
,
'cal
steel vessel-t having anannularchamber 2
I, therein. forming a jacket for the introduction
.ofyany desired heating “medium, as for example
steam, which may be supplied thereto bymeans
of a pipe 3 havinganinlet 4 connected to" the
bottom of the cylindrical vessel I, and'which
. may alsoserve as a means for drawingyofi any
centration of; ".03 gr. of vanadium oxide per cc.
' (.oiegr.
7
_ NaVOo per cc.).
The temperature‘ is
then raised to about 60‘ to 90° (3., but preferably
' 90", ‘by means of the steam and then maintained
in this range. ‘ The anode I7 is rotated at any
desired speed, but for example at about 1 R. P. M!
‘ Direct current'is then applied to the electrodes,
_ condensedtwater therefrom. The chamber 2 has 50
said' current being of any desired character,
but for example of 25 to 35 amperes per square
bottom'portio'n B providedwith-a conical lower
, -an_inner cylinder 5 connected toza ?at annular
. central portion 1, whichleads to a draw-off pipe
.8 havingavvalve '9'communicating with an out
letpipe ID. A porous porcelain cylindrical dia-,
phragm “is set into. the bottom of'the cylinder
.5 man annular concrete'layer l2, and a conical
continuation-of the said porcelain cylinder I l'ex
tends downwardly over the conical steel ‘bottom
foot of anode surface at _6 to S'volts. Theva
fnadium oxide, V205, is thus formed on the outer
‘ surface of the
l anode‘ I‘! and this'is' continually
being removed by the scrapers 35, 36 as the
anode is rotated, in a loose granular form so that
it falls’ to the bottom and is easily removed
through the valve 9, after which it can be ?ltered
, 1 and into the draw-off pipe 8 up to the position 60 and repulped by suspending it in water and wash
ing it in any desired manner. The end of the
ofthe valve 9. eThisporous'porcelain' diaphragm
electrolysis
is shown by a sudden drop of am
. cylinder II has, provided on the outside thereof,
_ a cathode chamber I3:in which there is a per
4 foratedvcylindrical steel sheet mywhich ’may,
instead, however, be of copper, carbontor'lvionel'
,metal, vto serve as a cathode‘,»which is connected
to an electrical conduit orwirewlS. Within the
porous diaphragm, cylinder ‘H’ there is' also
formed an anode chamber il?qhaving therein a
rotating, solid cylindrical ‘steel or iron anode- l7. -
The anode l1 may be made of some other metal,
‘for instance platinum, but not ‘so advantageously.
,;The anode .YIJ'may-be carried ‘on a shaft lsrwh'ich '
is rotated by ,means of .any suitable source-of
powervandhas, a conducting cylinder. thereon car
perage, at‘w'hich time the anolyte in'the cham
ber I 6 containing the ‘suspended vanadium oxide
is drawn off for'further'proces'sing, as‘ above re
65 ferred to.
The cell I6 can then again be ?lled
with fresh sodium vanadate solution and the
‘electrolysis repeated. The electrolysis of each
batch is preferably" continued, in the manner
above described, until about 75% of the vanadium
present is' precipitatedv as vanadium oxide, at
‘ which point the sudden drop in' amperage will
"take. place." Preferably, also, the precipitated
’ vanadium oxide is ?ltered to separate it from
the'mother liquor; Thereafter,_'it is then sus
pended in Water, as above referred to, in any.- de
2,606,148
6
5
caustic soda solution,,with a direct current den
sity of approximately 25 to 35 amperes per square
about 10 gr. of vanadium oxide per 100 cc. of
foot of the anode of 6 to 8 volts and a temper
water, and stirred at a temperature of about 90
ature of about 60-90° C., ?ltering oil the pre
to 100° C. for at least 3/4 of an hour. If the
vanadium oxide is precipitated from a sodium C21 cipitated vanadium oxide from the anode liquor,
repulping the vanadium oxide with water at a
vanadate solution containing the equivalent of
temperature of 90-100° C. for at least % of an
.06 gr. vanadium oxide per cc. of the solution or
hour and then ?ltering and drying the puri?ed
less, and if the vanadium oxide produced is re
vanadium oxide.
pulped under the conditions described above, the
3. An electrolytic process for obtaining vana
resulting dry vanadium oxide will have a purity 10
dium oxide, comprising subjecting an alkali
of about 97% V205, and will contain a minimum
metal vanadate Water solution to electrolytic ac
amount of sodium salts. The mother liquor con
tion with the aid of a steel anode so as to ob
taining the unprecipitated vanadium oxide and
tain a precipitate of vanadium oxide substan
other soluble salts, such as sodium uranate, may
tially free from iron at a concentration adjusted
be concentrated, cooled and treated to recover
to approximately .078 gram of sodium vanadate
vanadium oxide. The solution may then be ?l
per cc. at a pH of 7.0 and a cathode in a catholyte
tered and the vanadium oxide added to a fresh
of a weak caustic soda solution, with a direct
batch of vanadium bearing material in the oxi
current density of approximately 25 to 35 amperes
dized state. This mixture is then dissolved in
caustic soda solution to form soluble sodium 20 per square foot of the anode at 6 to 8 volts and a
temperature of about 60-90° C., the electrolysis
vanadate, as previously described for the prepa
being
continued until about 75% of the vanadium
ration of the anolyte.
present is preciditated as vanadium oxide when a
It will be understood that in conducting the
sudden drop in amperage takes place.
process, as the vanadium oxide forms at the
4. An electrolytic process for obtaining vana
anode the cathode liquor will increase in alkalin
dium oxide, comprising subjecting an alkali
ity. If desired, the catholyte in the chamber I3
metal vanadate water solution to electrolytic ac
can be drawn o? after each batch removal of
sired proportion, which may be, for instance,
tion with the aid of a steel anode so as to obtain
the vanadium oxide, or can be continuously re
moved by running water into the chamber H3 at
a precipitate of vanadium oxide substantially
water supply and allowing the caustic soda solu
tion which has been formed during the electrol
approximately .078 gram of sodium vanadate per
a slow rate from any suitable source of fresh 30 free from iron, at a concentration adjusted to
cc. at a pH of 7.0 and a cathode in a catholyte
of a weak caustic soda solution, with a direct
ysis, to overflow by means of the discharge pipe
current density of approximately 25 to 35 amperes
42.
square foot of the anode at 6 to 8 volts and a
The caustic soda which is produced at the oath 35 per
temperature of about 60-90° C., the electrolysis
ode can, furthermore, be used to dissolve a fresh
being continued until about 75 % of the vanadium
batch of the oxidized vanadium-bearing mate- '
present is precipitated as vanadium oxide when
rial, as for instance the uranium ore containing
a sudden drop in amperage takes place, ?lter
ing off the precipitated vanadium oxide from the
anode liquor, repulping the vanadium oxide with
water at a temperature of 90-100° C. for at least
3/;,‘ of an hour and then ?ltering and drying the
vanadium, above referred to. In this way, the
caustic soda necessary for the solution of the
vanadium-bearing material can be used over
again repeatedly in the process.
If desired, the vanadium oxide precipitated and
repulped as above, can be rendered anhydrous by
puri?ed vanadium oxide.
MARIO J. PORTANOVA.
ARTHUR ROSINGER.
drying, at a temperature of 300° C., for example. 45
While we have described our invention above in
detail we Wish it to be understood that many
changes may be made therein without departing
from the spirit of the same.
We claim:
\ '
1. An electrolytic process for obtaining vana
dium oxide, comprising subjecting an alkali
rr tal vanadate water solution to electrolytic ac
REFERENCES CITED
The following references are of record in the
50 ?le of this patent:
UNITED STATES PATENTS
,
tion with the aid of a steel anode so as to obtain
a precipitate of vanadium oxide substantially free 55
from iron, at a concentration adjusted to approxi
mately .078 gram of sodium vanadate per cc. at a
pH of 7 .0 and a cathode in a- catholyte of a weak
caustic soda solution, with a direct current den
sity of approximately 25 to 35 amperes per square 60
foot of the anode at 6 to 8 volts and a temperature
of about 60-90° C.
2. An electrolytic process for obtaining vana
Number
1,050,796
1,322,000
1,435,886
1,719,984
1,807,585
2,448,848
Name
Date
Bleecker _________ __ Jan. 21,
Ellis ____________ .._ Nov. 18,
Acton et al ________ __ Nov. 14,
Klein et a1. ______ __ July 9,
Becker __________ __ June 2,
Van Loenen _____ __ Sept. 7,
1913
1919
1922
1929
1931
1948
OTHER REFERENCES
“Comprehensive Treatise on Inorganic and
Theoretical Chemistry,” by Mellor, vol. 9 (1929),
"
“Transactions of The American Electrochemi
metal vanadate water solution to electrolytic ac 65
cal Society,” vol. 30 (1916), pages 175-221.
tion with the aid of a steel anode so as to obtain
“Electrolytic Oxidation and Reduction,” by
a precipitate of vanadium oxide substantially free
Glasstone et al. (1936) , pages 114-117, 333, 334.
from iron, at a concentration adjusted to approxi
“Kolloid Zeitscrift,” vol. 30 (1922), pages 346
mately .078 gram of sodium vanadate per cc. at a
348,
.
pH of 7.0 and a cathode in a catholyte of a Weak 70
dium oxide, comprising subjecting an alkali
pages 750, 753.