A PROCESS FOR THE CONTROLLED LEACHING OF NATURAL MANGANESE DIOXIDE BY USING HYDROCHLORIC ACID

METHODE POUR LE LESSIVAGE CONTROLE DU DIOXYDE DE MANGANESE NATUREL GRACE A L'EMPLOI DE L'ACIDE CHLORHYDRIQUE

English Abstract

The present invention relates to a new
process for extracting and recovering natural manganese
dioxide (NMD) deleterious matter by using a hydrochloric
acid solution as leaching agent, which process is
carried out in a sequence of equipment the control
devices of which are calibrated in such a way that the
mixture contained in the leaching machine must have a
pulp density of 10%-40% weight, a hydrochloric acid
concentration between 9% and 25% weight, a temperature
between 89°C and 95°C, and a leaching time between 10
and 60 minutes resulting from the interaction of certain
values, these variables being limited, wherein the
amount of deleterious matter and MnO2 to be extracted
and recovered according to expected results shall be
defined.

Claims

8
CLAIM
1. A process for controlled leaching of impurities from natural
manganese dioxide by using hydrochloric acid, wherein a hydrochloric acid
solution is used for leaching natural manganese dioxide, which leaching is
controlled by equipment calibration in such a way that the interaction of the
effects thereof forces the hydrochloric acid concentration to be within a
range
between 9% and 25% weight, the temperature during the reaction within a range
between 80°C and 95°C, the pulp density within a range from 10%
to 40% w/w,
and the leaching time within a range between 10 and 60 minutes.

Description

y LW uq~~
.. f.~ F'F;nLI= ~~ F~nF, TI-JF GLtf~J~TF:(11_l...EI) L_E.llt~;ld I t~1(~ C!F
PJI~IT'l.IF;IIL..
t-lElfidCAt~l~SF D t Q X I L)C.-'- F>'i 1.1 ~ I tdt~ f r'rI)r coc:nJl_..c7r z
c; IBC 1. ~ ~~
1'he pre. sent 5.roventa.arn refer- to ~ pr-csce~s
f,ar- e;:tr-acting and r-er_t:?~~rer~-.ing natr..rr-al. rnang.-~nr~?s~
da.a:;i.d~

CA 02144925 2004-08-31
2
(NMD) deleterious matter under the action of a sequence of equipment which
control previously defined physical-chemical conditions.
More specifically, the present invention relates to a process for
controlled leaching of impurities from natural manganese dioxide by using
hydrochloric acid, wherein a hydrochloric acid solution is used for leaching
natural manganese dioxide, which leaching is controlled by equipment
calibration in such a way that the interaction of the effects thereof may
force the
hydrochloric acid concentration to be within a range between 9% and 25%
weight, the temperature during the reaction within a range between 80°C
and
95°C, the pulp density within a range from 10% to 40% w/w, and the
leaching
time within a range between 10 and 60 minutes.
The -state 'off the art points to the
possibility of preparing a synthetic manganese dio;:ide.
Electrolytic manganese dioxide (Ehl~?) is obtained from
the electrolysis of ~ h1n80~. solution whose raw material
:is rtn~l~~ or MnCO~. Chemical manganese dioxide (GMD) is
~:~~=.a obtained t~~~ precipitating MnO~ into a manganese
solt_ttion (oxidat.ion or' divalent manganese salts) .
I--lowever, the P~in0:~ ltraching wherein the natural. dioxide
G:tr!.tct!.tre is b;ept and the I~MD heavy metals ~tre
eliminated is not known in the indt_lstr-y.
The composition of manganese are varies ~r~cacr,
recrivn in the continents and urrder the sea. In vieua o~
thnt~ in addition to already a>;isting treatnvents,
certain countries are concerned at~or_!t sea nodules and
tia~re de~reloped teci-vrsiques for reco~:ering the metals
Present in manganese matrices (Nia Go, Mn~ among
other=_.), trtwatmGntC. and techniq!.!es still ineT~icient in
the case of s?gnificant mmnganese ore occ!.trrence.

CA 02144925 2004-08-31
2a
Tne ~~mr-~~o~e c~f t~~ pr-~=.~.nt pr oce=~ x~ tc~
Gacccynyli~~M~ the ~c.r-~~-~tm~nt t~f n~~cur-~i mC~ngane~~ di«::ide
(fVi~l~) .~.n et cr~n~a=~-r:a.~:nt ~~ay not t~et contemplated by rt7e
~. t ~~x t c= n f ~t. I-m~ ~ r- t
In tie Gsqinninq9 a>;~ioi.tatic~n tests Tor-
Ic~~cioa.ng ~oPaD icy using n~~dr-ec.inlcaric a.r_zd wPr-e cnndttcted~

21449~~
whose main object i.s the eventual occurrence of
E:~referential salubilization of deleterious matter (Cu,
Ni, Fe, Ca) with resper_t to the t~ir~02 matri;;. Variables
s~.tch as temperature, HCl concentration, reaction time
and the reuse of the filtered hydrochloric liquor were
taken into accav-mt when such tests mere performed . I t
can be nati.ced that all these parameters are important.
The solubilization of the many components
t:rresent i.n the manganese matri;; was considered to be
rather important because the concentration of a mineral
by the leaching process is attained by salubilizing the
impurities.
After having defined statistical results,
aptimi'ation tests were then scheduled, which tests
included the pulp density, in view of the importance of
this variable in industrial plants. At this optimization
stage, it was determined which effect four independent
variables (HC1 concentration, temperature, leaching
time, pulp density), which change at the same time, have
on dependent variables (Mnaz regeneration and Cu and Ni
content in the concentrate).
At this final evaluation, with respect to Cu
and Ni and the tHnOx regeneration, the effects of the
many independent variables and the interactions thereof
were confirmed. Most importantly, the importance of the
HCL concentration and the temperature with respect to
the other variables was demonstrated.

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i.lPtimi~ed assays st-,awed the follawinQ
CGndltl.anal Vc~lUeS:'
- HGL ct~rtcentratian - 9°!. to ~~ ~ weic~t-~t,
depending on the e.;pected e:~tr~~ction of deleteriaue.
~rmtt:.er and i~ln~-~ regenEtration.
.._ ~erxching time = 1e to ~O minute's depending
an thc~ es;pected c;traction of deletc~r-inu~~ matter- and
MnO~= rec~ener-ation.
-- ~E?trtpere'ttl_tY'~ - ~~1'='G tQ ~~'~Cq wherelrl the
limit i~ 9~"C because it is c~ui-te difficult tc~ hmndle
HCwl abave said temperature due to it=_. vapor ternsic'n acnd
c~::idicing power.
Pulp density = 1t~% to f+~~f weight, de~~ending
cm th~,5 Hi.:l cancentratinn used in the pracees.
Eimanct s.ai.c9 ronditian~ea ua7.ues, =.c"z:e aptirr~i~atians are
c7ivPn in the table beiawe
t°~no~f~::~ l~Jif PP;n) t~uipCm) ~-~ec~c--~n,.MnQ:~('I"t
~C3'~ore 87e~~:1 .;,t=>i=i -
leacha.nn
(~c,t,'_rni~ed 8~ to .~~~ to i~{n to 7;i to ~~~
'~.. C"' -> 1.. ~l a,:. v'.:i 5 ~ G~ f
Figure '! in shECt ? of the appended drawing
~.i~ot~a~. the 7l.ar~a-chart of the L~-~ea.c eqv_;:~.p«mewt designed

CA 02144925 2004-08-31
-i~c~r ~~::trC7ctinc~ deleterious rn~~tter -i~rom r«tur-al ma~nc~ane~E
c1 i.a;: i.de ( hal"1I:1 ) . The p~cr~t= therea-~ ~u~E numbered ~s
fallawee
1.. convector Melt
~t9~~ dispensing silo
-.. water- and hydrochloric acid reservoir
pa.pe fitted with dispc=nser-
carnveyc~r t~eJ.t
cx. ie~chinr~ tang;
i. mntar
9.. rni:ar-
heater
1«. mortar--pump
1.t. canduit (piping ar cup hoisti
1~..'. filter
_t._~. F~iping
14 . ct~ai one 1
.A.5. ;rlDtai"'
lr.~. dr-utn dryer
1 ~ . carnve~; err-
s-ic~corcJinca to i:.he fJ.c~~?-ct-:arty thF a>;trac4iaru
o~f delctcr-iuu~=_. rrmt_ter- fr-arr, r°~~tmr-~i rr3;ung~~n~,~.e
dia~;idF,
(IV~1I:~1 i.~. ~ccam~~:kished throi_ic~h the fallw?lnr~ wa~ic: step5~
F°art of the di~pender- cc~ritr-c_~1 i~~c:
ii'ydr-C;~ChI.C?r-1C =(C:3.d etnd w:3'E.~1" ~.Cil~ltlar't CarnCEtln~d 1f-s
'Li'i
rc~E~;w~: wir ( . ) is pmxred an tile tan i~; ( ~:~ ~c.i-~r-a~_yi-~ the:
piF,~,
(~~ . T h~: i-ve~Ler~ i= t!~rn~:d an, ~:nd ~ certain amount a~

CA 02144925 2004-08-31
6
milled nats_!raI manganese dio.;ide (1'~It~1D) de~a=_.itec.! in the
i.:i i~.pe~nser- si 1w ( ~ ) is ~,aured cfr~ tt-m tang.: ( 6 ) by the bel t
( 5) when the temperat!.!re re~.~ches ~ present v~~xlue. The
cJF_e..irad ~aulp density being tiwus attaa.ne~d, the ni~tc~r (~')
a~ ~,c:~tuated~ then driving thc~ mi>;Pr (8i dur-:ing the
t~~er~ie~ci define.5d fc:r tt-mr leaching to terminate. It is then
that thc~ motor--~umy ( ,Ir.~) i s aet to ~~~rk: , thin conveying
the lEc'tr=1-ve~I ~.,rr~duct tlurnugh the cond!.!it ( 1.1 ) tow~erd~ the
fili;rr (l:~'). flftNr the whsle pui~ i= filtered, the !_ak:e.
falls into tt~e ch~7nne1 (.i~) and then goes through the
car°s.snz dryer (1b) which ice'. driven by the motor (1~) ~ the
fi.lt:F~r-wd hjdr"GCI-:lc~ric liquor rcturn~. to tt-:e (6) t.tnra~.!c~h
the pi.Eae (i~'.)" Anc,ther- c~~cle similt3r i=c.-r the cie~~cr.ibed
cane i.s ~~erted then .
-i'he resmi~.: Gf the ~~.scces~i~.~E utilaz~-,tic_,n c~f~
the h~,rciroct-u.t~aric li.s~mor, in ~dditicn tc~ increment t_he
rc~nc~e:ntr~ct:ic:rt of he.~vr met~;lc. - which i.C. fsr!ndam4ntal to
the. m!i~se:l!_tent a>;tr~ction thereof b~f r_hemi r_el and (car)
elEet.rr~civemic.~sl meajn= - is. an ini=re~,se in the
seier_~tiwi~t_, oaf thr solubilization of .aid metals Gaith
:~e~.[~F.=ct tC~ r~iri~~ . ~"IC~~J~Ye F" n a.t eve.r~,: neua c~; C 1. e, the
cc~rcvGl ernervt~r;f ricditior~. ~,-~ the 1-I!.,1 1- i-i~Ct si;lt!tion
contains in the r-es.er~~,~nir- (~ ) fc~r rnaintsininp the=
ae-s;~:i;ir°vg acier~t t cc.~r~cerntratic,n w~usi: be carr-ic~l out.
The described naturJ~1 rnan!~anet=a dir=:.;t~ivs
i,rwi=tL5 j ~urifi.ceti,~,r~ t-ms t.i-~~~ f~,11GV17ng mdvantaqes s~~ith
r ~,~~~~...~_. .t~.~ s~icJ impure s:;etal

CA 02144925 2004-08-31
_.. The, a>;tr~-tctic~n of heavy metals ma4;e~ it
Faa=_.s.~.~7.e rc~ use hl~dI? far tire n;ar,u-iwr_tmre of mereuryless
electrc~lytic,~l batteriES - which is thc3 wardwide
tendency in view of ermiranment~-rl pr-at~lems.
- The ir~r_rease in tlve content of t'tn0,~
z.ncreasc~s the electrochemical battery durability;
- There is a 3tranw irvdus:trial Gtnd carnmerei~tl
demand fur- the other products e;:tr-ac1_ed in them
pura.ficatiari stages. Tt-ws, frGrn frnCDYt~ we car- c~t~tain
t~It~Gl~t besides fuel additives. Ni. W.v and Go are hi.r.~i-~
valued metals due to the: f::cct that tYSej or a a=.ed in
sp~:vci~~lited indu=.tries.

Representative Drawing