Àug- 3, 1943~ E. M.

wANAMAKs-:R _E1-AL 2,325,723

PURIFICATIQN IN ELECTROWINNÍNG 0F MANGANESE '
vwed Feb. 2v, 1942 1

A rroßn/Ey;
 Patented .Augr 3, ì .2,325,123

"UNITED ` lSTATES PATENT tz(_)l"`l",'IClÉ`.r- '

_ ' 2,325,723 y y _ ‘ ` .,

PURIFICATION 1N ELECTROWINNING 0F
'n MANGANESE _ _ l

Elmer M. Wanamaker and William D. ‘Morgam »

Jr., Knoxville, Tenn., `>assignoi's _to Electro
«'Manganese Corporation, Minneapolis, Minn.,
acorporation of Delaware - ~
Application February 27,' 1942, Serial No. 432,692 j
l - 2 Claims. i (Cl. 204-105) I f 'v „

' The invention i‘elates to 'the electrowinning of the sulphur as ammonium 'sulfide by Cabsorption
rmanganese, more particularly the puriñcation of , of the HzS evolved in aqua ammonia. „Y- '_
electrolyte to be used as the catholyte. . This process has certain disadvantages which
In the electrowinning of manganese, theelec it is the object of the present invention to .over
rrolyte is divided into analyte and camente. 5' come. The recovery of manganese from the mud \
Anolyte is continually withdrawn from the ano~- is troublesome and expensive. The use of the
lyte chamber and used for the extraction of man large excess of ammonium suliide represents an
ganese from manganese ore, the anolyte being y _ economic loss and in turn, re'sults in an excessive
thereby enriched in manganese. At the same precipitation lof manganese as sulfide in the mud. -
time, however, impuritiesare introduced into the 10 `^ Moreover the- purification which is the objective
extract from the ore, among which iron,- arsenic, of the use of this large excess of ammonium sul-A
antimony, nickel and ’cobalt may be mentioned. ' ilde is incomplete and'this incomplete puriiication
The iron, arsenic and antimony are commonly re reflectedin the quality of the cathode deposit.
moved by oxidizing the iron `Ato the ferrie condi ~ In addition ’to nickel and cobalt there are other
tion, following which and at a suitable DH, iron .15 impurities the removal of. which is desired'and -
is precipitated, together with arsenic and anti the efiect of which is evidenced “by the physical
' ‘ >mony if a sufiicient amount of iron was present character of the deposit as a whole as distin--
in solution. Following the precipitation of‘the guished from the Presence of~ nickel and _cobalt
iron, ammonium suliide is used> as a reagent for as metallic impurities in the deposit. . -
the precipitation oi' other impurities, such as 20’ For example, one of the disadvantages isthe
nickel, cobalt and copper, in Äthe form of their tendency of _the deposit, during formation 4and
suliides. Thenickel and cobalt precipitated in ydeposition on the cathode, to peel or crack and
the form of a sulñde mud is separated by illtrai in someinstances to actually fall of! in the catho
tion or otherwise and the filtrate then goes to lyte chamber, in contrast to the desired character
the catholyte‘ chamber of the cell, thus complet- 2Q of the deposit which
7 is a coherent coating sum
ing the cycle oi the movement and treatment-of ` ciently adherent lto the cathode to permit its re
the electrolyte, beginningI with the removal of moval with the cathode ,from the cell prior to
anolyte from the anolyte chamber and ending- the subsequent treatment of the cathode to sep
with the introduction of catholyte into the catho -arate the metallic manganese deposit. The pre
lyte chamber. This cycle is_ continuously re- 30 oise nature of these impurities has not been
l peated. Y
vdeiinitely established although it is believed thatí
In the process following this cycle, on which, l, they are of a colloidal nature and therefore pass
the process of the present invention is an im through the iilter-membrane. It is believed that
‘ provement, a large'excess oi ammonium sulfide they comprise colloidal silicates and compounds
over that theoreticallyr` necessary to precipitate 35 -of manganese, cobalt and nickel in dispersed
the ~nickel, cobalt vand other elements whose S111 form. f ,_ ,

iidesïare insoluble in the given solution, is u'sed. Y . It has been discovered that the stated disad
For example, to -a batch of 32,000 liters of an vantages can be largely if. not wholly overcome
electrolyte from which the iron, arsenic» and. by effecting the precipitation of the nickeL'co
_ antimony have been precipitated, containing 20 40 balt; etc., in each Icycle in the presence of a large
to 50 grams per liter of manganese as manganese excess of sulli'de mud obtained _in-,a previous
“ sulfate, ammonium sulfate 140 to 180 grams per , cycle. For example, to the extract from which
liter and which may have a pH of about 7.2‘ to iron, arsenic, -antimony and the like have been
‘7.5,` about 60 liters ci' a saturated solution of - removed there may be added,_at_ a. pH of about
ammonium sulfide are added.- The'púrp'ose of ‘f5 '1.2 to 7.5', not only ammonium suliide but also
using .this large excess o1' ammonium sulfide is to suliide mud froml the next preceding cycle and r
precipitate the nickel, cobalt, etc., as sulildes as' _ the precipitation of nickel and cobalt'thereby ef
completely as possible. Owing, however, to this iected in the presence ‘of that mud. This proc
- large excess, substantial quantities of manganese ess is then repeated in each succeeding cycle, sub
sulfide are also precipitated. . - 0 stantially the same body of mudbeing continu
The mud, which may contain as. much as> 5 ously reused in the successive treatments or
gement of the manganese in the ore treated, is A cycles. Analyses indicate the possibility that'the "
ither discarded entirely or submitted to a, process composition olfV this 'body> of mud in these suc
comprising treatment'with sulphuric acid to re _ cessive‘ treatments progressively changes, the ..
- I cover the. manganese as manganese sulphate and ‘55V nickel and cobalt> content progressively increas
 2 . 2,325,723
ing and the manganese content correspondingly tional or excess suliide mud precipitate caused by
decreasing. In such change in composition, a the addition of the 15 liters of ammonium suliide
point might be reached at which the cobalt and are siphoned oil.’ through the riser I9, line I3
nickel content of the mud reaches a value inak provided with valve 29 and line 3i, and ñltered in
ing possible the economical recovery. of the nickel the ñlter press 32. _The filtrate is passed through
and cobalt Vfrom the mud. Furthermore, such a the line 35 to catholyte storage tank 4I and
progressive decrease in manganese content would thence through the line 42 to the catholyte com
constitute in eifecfl an automatic process of re partment 39 of the manganese electrowinning
covery whereby the manganese is transferred cell 40. The precipitate of excess suliide mud
from the mud .to the electrolyte thereby obviat 10 iilter cake from the filter 32 (corresponding to
ing, to' thev extent to which this occurs, any sep the 15 liters of ammonium sulfide) is then passed
arate and independent step of recovering man- _ through the line 36 to the mud storage tank 31.
ganese from the mud. In order to avoid too During the treatment of the contents .of tank
great an accumulation of mud, a fractional part I1, another batch of 32,000 liters of extract is
thereof may be removed in each precipitation and 15 passed from tank 6 through lin'es 9 and I2 pro- `
discarded or subjected to a process for the re vided with valves I3 and I4 into treatment tank
covery of the manganese and other constituents 23 and the treatment therein is the same as that
therein. However since, except for this frac described above in describing the treatment of
tional portion, the mud is used over and over the contents of tank I1, suliide mud being ini
again, the lossl of manganese in the event that 20 tially supplied to tank 23 from mud storage tank
the excess mud is discarded is greatly reduced 31 through line 45 and line 41 provided with
and the expense and trouble of recovering man valve 48 and thereafter maintained in said tank
ganese from the excess mud is also reduced. In up to the level 25. The supernatant liquid to
addition and perhaps most important of all, the gether with excess mud up to the level 24 is with
character >of the cathode deposit is improved and drawn from tank 23 through riser ISA, lines 22
it has been found thatby proceeding in accord and 3| and ñltered in ñlter 32, in the same man
ance with the present invention it is possible to ner as described in connection with tank I1.
constantly and uniformly obtain smooth adher It will thus be seen that in each of the tanks
ent deposits free from the previously uncon I1 and 23 a substantially constant _quantity or
trolled endency to crack and flake 0E. It is to volume of suliide m'ud is maintained, indicated
be noted that this phenomenon of peeling and in the drawing by the level lines 2l and 25, re
flaking oi‘î is to be distinguished from the phe . spectively. The only portion of the suliide mud
nomenon of receding which occurs in the absence which is withdrawn from these tanks is the ln
of adequate control over cathode potential. creased quantity produced therein by the suc
The principles of the invention will be defined 3 cessive additions of ammonium sulfide (passed
in the claims and a specific illustrative embodi through lin'e I5 providedwith valves I6 and
ment will be described in conjunction with the ISA) in the successive treatments.
accompanying drawing showing diagrammati The two tanks I1 and 23 alternate in their
cally a ñow sheet illustrating steps in the proc functions; that is, while extract is being. purified
ess of the invention and apparatus which may 40 in one tank puriñed supernatant liquor is being
be employed in practicing the same. siphoned oif from the companion tank and de
' Anolyte having a composition of 10 to 18 grams livered to the catholyte storage tank 4I, so that
per liter of manganese as manganese sulfate, the catholyte storage tank is being continually
about 140 to 180 grams per liter of ammonium replenished with puriñed catholyte. There is
`sulfate and a pH of about. 1 to 2 is withdrawn 45 always available, therefore, one tank having a
from the anolyte chamber '38 of the cell 40 and suitable body of mud therein into which to
passed through line I to the ore extractor or di charge- iron-free extract for purposes of puri
gester 2 where, by agitation with suitable man fication. As many separate purification tanks as
ganese ore, the concentration of manganese in desired may be used. v
the extract is raised to 20 to 50 grams per literl 50 Whereas-in the process in respect of which the
and the pH raised to about 2 to 5. The pH of present invention is an improvement, it was
the extract is adjusted to about 5.5 to 6.0 and air necessary toV employ about. 60 liters of 45% am
or other suitable oxidizing agent employed to monium suliide for each successive batch of
oxidize theiron to the ferric condition and cause about 32,000 liters of iron-free extract, the
the precipitation thereof along with arsenic, an present invention makes it possible to reduce the
timony and the like. The precipitate is then ñl ammonium suliide down to at least 15 liters;
tered in the filter 4 and a volume of filtrate equal and whereas in said previous process it was
to about 32,000 liters is passed through the line 5 necessary to discard the entire suliide mud
to the tank 6 where the pH is adjusted to about precipitate or work it up for recovery of manga
7.2 to 7.5 as, for example, by thè addition of am 60 nese and other constituents, according to the
monia added through the line 1. The contents present invention, except for the increment of
of the tank 6 is then 'passed through the line 9 sulñde mud removed as herein described, the
provided with valve 8 to the tank I1 in which is said suliide mud is used over and over again
retained ¿sulfide mud .(from the previous purifi in each of the tanks I1 and 23 and the quantity
cation) to level 2l in the tank, the quantity of 65 of mud which it is necessary to work up for
mud being approximately that which would be vrecovery purposes or discard is very greatly re
obtained by adding 60 liters of 45% ammonium ` duced. Finally and perhaps most important,
sulfide solution to 32,000 liters of iron-freetex the continuous reuse of the mud in the precipi
tract. In addition, 15 liters of 45% ammonium tation of nickel and cobalt eñ'ects such a puri
suliide are added to the contents of the tank I1' ilcation of the electrolyte thatpthe cathode de
and the entire contents are then suitably agitated posit obtained therefrom is substantially free
and then permitted to settle. A quantity of from the disadvantage of cracking and peeling. _
mud, in addition to that originally in the tank Although the precise mechanism by which the
. I1, is formed and is indicated by the level line 20. purifying eilîect of thé mud is obtained is not
The supernatant liquid, `together' with the acidi 75 fully known, it is believed that it exercises@
 2,325,723
unique adsorptive eiTect or other physical
chemical .action by which the colloidal im
purities which are believed to contribute tothe
cracking and peeling _of the manganese cathode
deposit are removed.
' Instead of ammonium sulfide, which is pre
ferred, it is possible to use- soluble sulñdes in y
general.
We claim:
f 1. In a cyclical process for the purification of l0 ~containing nickel suliide, cobalt sulildel and
catholyte in the eiectrowinning of manganese
in which ore is extracted with anolyte and the`
extract is treated to remove iron and then with
ammonium sulfide to precipitate nickel and co
balt as suliides, whereby a sulfide mud is ob
tained containing nickel suliide, cobalt sulfide
and manganesesul?de, the mud' is separated
from' the solution and the latter is. used as
catholyte, the improvement which comprises
precipitating cobalt and nickel suliides by add 20
ing ammonium sulfide in the presence of sulfide 5
mud obtained in a previous cycle,- and thereby
_ , 3
forming an additional quantity of mud, the pro
portion of said mud obtained in a previous cycle.
being in excess of said additional quantity.
2. In a cyclical process for the purliication of
catholyte in the electrowinning of manganese
in which ore is extracted with anolyte and the
extract is treated to remove iron and then with
a soluble suliide to precipitate nickel and cobalt
as sulñdes, whereby a suliide mud islobtaincd
manganese sulfide, the mud is separated from
the solution and the latter is used» as catholy'te,
the improvement which comprises precipitating
cobalt and nickel suliides by adding said soluble
suliide in the presence of sulfide mud obtained
in a previous cycle, and thereby forming an ad
ditional quantity of mud, the proportion of said
mud obtained in a previous cycle being `,in exs
cess of said additional quantity. y
M. WANAMAKER.
WILLIAM D. MORGAN, Jia