IE84218B1 - Treated manganese ore, process for producing the same, and use thereof - Google Patents
Treated manganese ore, process for producing the same, and use thereof Download PDFInfo
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- IE84218B1 IE84218B1 IE2001/0338A IE20010338A IE84218B1 IE 84218 B1 IE84218 B1 IE 84218B1 IE 2001/0338 A IE2001/0338 A IE 2001/0338A IE 20010338 A IE20010338 A IE 20010338A IE 84218 B1 IE84218 B1 IE 84218B1
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- ore
- manganese
- treated
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- manganese ore
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- 239000011572 manganese Substances 0.000 title claims description 333
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 323
- 229910052748 manganese Inorganic materials 0.000 title claims description 323
- 238000000034 method Methods 0.000 title claims description 74
- 230000001603 reducing Effects 0.000 claims description 136
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 111
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 93
- 238000006722 reduction reaction Methods 0.000 claims description 76
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 238000004090 dissolution Methods 0.000 claims description 63
- 239000007789 gas Substances 0.000 claims description 58
- 229940099596 manganese sulfate Drugs 0.000 claims description 57
- 239000011702 manganese sulphate Substances 0.000 claims description 57
- 235000007079 manganese sulphate Nutrition 0.000 claims description 57
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 57
- 229910052742 iron Inorganic materials 0.000 claims description 46
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 44
- 239000011591 potassium Substances 0.000 claims description 44
- 229910052700 potassium Inorganic materials 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 25
- 238000007654 immersion Methods 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims description 2
- 230000001590 oxidative Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000002893 slag Substances 0.000 description 16
- 239000007858 starting material Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005063 solubilization Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052935 jarosite Inorganic materials 0.000 description 5
- 229910000468 manganese oxide Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese(II,III) oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940105305 Carbon Monoxide Drugs 0.000 description 2
- 229940044609 Sulfur Dioxide Drugs 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N Tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000012970 cakes Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 e.g. Chemical compound 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired Effects 0.000 description 2
- 229910000460 iron oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 241000521088 Coua Species 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N Iron(III) oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- ZSKCOFJBFXSEDP-UHFFFAOYSA-N formaldehyde;molecular hydrogen Chemical compound [H][H].O=C ZSKCOFJBFXSEDP-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon(0) Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Description
TREATED MANGANESE ORE,
PROCESS FOR PRODUCING THE SAME, AND USE THEREOF
FIELD OF THE INVENTION
The present invention relates to a treated manganese
ore for use in producing manganese sulfate therefrom, a process
for producing the same, electrolytic manganese dioxide obtained
therefrom, and a process for producing the manganese dioxide.
More particularly, the invention relates to a treated manganese
ore in which the manganese is highly soluble in sulfuric acid
and the potassium content can be reduced according to need
and which is suitable for use as a material for a manganese
sulfate solution to be used in, e.g. , producing electrolytic
manganese dioxide therefrom. The invention further relates
to a process for efficiently producing the treated manganese
ore and to electrolytic manganese dioxide produced from the
same.
BACKGROUND OF THE INVENTION
Manganese sulfate is a useful compound extensively
used not only as a starting material for electrolytic manganese
dioxide for use as a dry-battery material but as an industrial
intermediate chemical forlferrite, pigments, ceramics, etc.
Amanganese sulfate solution reduced in ‘impurity content
has conventionally been obtained from a naturally occurring
manganese ore through the following steps: 1) a reduction step
in which a naturally occurring manganese ore is reduced at
a high temperature to obtain a reduced manganese ore, 2) a
dissolution step in which the reduced manganese ore is dissolved
in sulfuric acid to obtain a crude manganese sulfate solution,
and 3) a purification step in which impurities are removed
from the crude manganese sulfate solution to obtain high—purity
manganese sulfate.
These steps will be explained below in order.
) Reduction Step
Manganese oxide can exist in various forms according
to the oxidation state of manganese. In naturally occurring
manganese ores, such manganese oxides of various forms coexist
with each other in various proportions . Since manganous oxide ,
among those, is the only manganese monooxide which completely
dissolves in sulfuric acid, it is necessary to reduce a manganese
ore to manganous monooxide prior to dissolution in sulfuric
acid.
In Tetsu To K6, Vol.49, p.971 (1963) and Tetsu To K6,
Vol.49, p.lO59 (1963), there are descriptions to the effect
that although manganese ores can be reduced at a temperature
of 400°C or higher, reduced manganese ores obtained through
reduction at a temperature as low as 700°C or below have a
drawback that they have poor storage stability and are apt
to form acid-insoluble matters when stored in an ordinary way,
resulting in a reduced degree of manganese dissolution in
sulfuric acid, and that for obtaining a stable reduced manganese
ore, it is necessary to conduct the reduction at a temperature
of 700°C or higher, preferably about l,OO0°C.
JP-B30036 (the term "JP-B" as used herein means
an"examinedJapanesepatentpublication")disclosesthatwhen
reduction for obtaining a reduced manganese ore is conducted
by heating at l,093°C or higher, ore grains sinter, making
the processing difficult.
Consequently, JP-B4498 and.IP-B30036«disclose
that the reduction of'a manganese ore suitable for industrial
use from the standpoints of the degree of manganese reduction,
rate of reduction, stability of the reduced manganese ore,
heatresistanceofovens,andoperationstabilitycanbeattained
by reducing a pulverized manganese ore at a temperature as
high as from 800 to 1,000°C in the presence of a reducing agent
such as methane gas, hydrogen gas, or carbon monoxide for a
period sufficient to convert manganese oxides into manganous
monooxide. However, reduction at such a high temperature of
from 800 to 1,000°C necessitates use of—a castable refractory
material or heat-resistant tungsten steel as the material of
the reducing oven, making the apparatus highly expensive.
) Dissolution Step
Inthedissolutionstep,thereducedoreobtainedthrough
reduction in the reduction step described above is added to
and dissolved in sulfuric acid to obtain a crude manganese
sulfatesolution. Inthisoperation,metalsoruetalcompounds
such as potassium, iron, and cobalt contained as impurities
inthereducedorearealsodissolvedtogetherwiththemanganese.
The degree of manganese dissolution in sulfuric acid in the
dissolution step has been lower than 98.0% by weight based
on the manganese contained in the treated manganese ore.
Such a low degree of manganese dissolution from the
reduced ore leads to poor profitability and has been an important
subject in industrially practicing the process . Furthermore,
the low degree of manganese dissolution results in the generation
of a large amount of manganese—containing slags, which are
difficult to utilize. The slag generation poses a problem
concerning environmental preservation and has also been an
important subject in industrially practicing the process.
) Purification Step
In the purification step, iron and various heavy metals
are removed from the crude manganese sulfate solution obtained
in the dissolution step described above, by precipitating these
impurity metals by treatment with, e.g., hydrogen sulfide.
Thus, the manganese sulfate is purified. However, it has been
exceedingly difficult to remove the potassium present in the
crude manganese sulfate solution by the conventional method.
If the potassium comes into electrolytic manganese dioxide,
it exerts unfavorable influences on the performance of the
dry battery. Although the following methods for potassium
removal have hence been proposed, neither of these has been
satisfactory.
a) Jarosite Method
In JP—A—60—l6623l (the term "JP-A" as used herein means
an "unexamined published Japanese patent application") is
disclosed a method which comprises adding trivalent iron to
a manganese sulfate solution, adjusting the pH of the solution‘
to thereby precipitate the potassium contained in the solution
as jarosite [K2Fe5 (SO4)4 (OI-I)12] , which is a double salt of
potassium and iron with sulfuric acid radical, and removing
the precipitate by filtration. Although this jarosite method
is effective in relatively easily removing potassium, it has
problems that the potassium concentration of the manganese
sulfate solution obtained by this method is still higher than
the level currently required and that the jarosite is difficult
to remove by filtration. This method further has the following
problem. After the formation of jarosite, a neutralizing agent
shouldbe added to adjust the pH to around 7 in order to precipitate
and remove the excess iron. It is generally known that a
manganese ore is used as the neutralizing agent. However,
when a manganese ore is used, the potassium contained therein
dissolves in the manganese sulfate solution to increase the
potassium concentration which has been lowered.
b) Water Leaching Method
Methods for removing potassium from a reduced manganese
ore prior to dissolution in an acid are disclosed in JP—A—4—'I4'72O
and JP—B—47—2424. Specifically, the former discloses a method
comprising treating a reduced manganese ore by heating it in
an alkaline aqueous solution at a temperature of 80°C or higher,
preferably 100°C or higher, while the latter discloses a method
comprising treating a reduced manganese ore with hot’ water
having a temperature of 100°C or higher. However, the method
in which a reduced ore is heated in an alkaline aqueous solution
necessitates a large amount of an alkali, resulting in poor
profitability. On the other hand, the method using hot water
necessitates a large, expensive high-pressure—resistant
apparatus because of the leaching temperature of 100°C or higher
although no chemicals are necessary. Thus, industrial use
of these conventional methods for water leaching has serious
problems concerning profitability and apparatus.
SUMMARY OF THE INVENTION
The invention has been achieved in order to overcome
various problems of the above-described conventional techniques
for the production of a manganese sulfate solution.
Specifically, an object of the invention is to provide a treated
manganese ore for use in manganese sulfate production therefrom
which has a high degree of manganese dissolution when dissolved
in sulfuric acid and which can hence be effective in reducing
the amount of slags generating in a production step and can
be reduced in potassium content according to need. Another
object of the invention is to provide a process for producing
the treated manganese ore easily and economically. Still
another object of the invention is to provide manganese dioxide
which is produced from the treated manganese ore and is useful‘
in primary batteries, secondary batteries, etc. A further
object of the invention is to provide a process for easily
producing the manganese dioxide.
The present inventors made intensive investigations
ontheproblemsofconventionaltechniquesinordertoaccomplish
subjects concerning the production of a manganese sulfate
solution. As a result, they have found that a reduced ore
obtained by reducing a manganese ore under skillfully regulated
conditions has a higher degree of manganese dissolution in
sulfuric acid than any conventional reduced manganese ore,
and that a novel method comprising treating the reduced ore
with warm water gives a treated manganese ore having an
exceedingly low content of potassium soluble in sulfuric acid.
They have further found that this treated manganese ore can
be easily obtained. Furthermore, the inventors have found
that manganese dioxide useful in primary and secondary batteries
and other applications can be easily produced from the treated
manganese ore having excellent properties . Thus , the invention
has finally been completed.
The invention provides a treated manganese ore for
use in producing manganese sulfate therefrom, the treated ore
having a degree of manganese dissolution of 98.0% by weight
or higher based on the manganese contained in the treated
manganese ore when dissolved in sulfuric acid. The invention
further provides a process for producing the treated manganese
ore which comprises bringing a manganese ore as a starting
material into contact with a reducing gas at a temperature
of from 400 to 790°C to obtain a reduced ore and optionally
immersing the reduced ore in water having a temperature of
from 70°C to the boiling point thereof as measured at atmospheric
pressure. The invention furthermore provides manganese dioxide
for use in primary batteries and secondary batteries which
is obtained from the treated manganese ore having such excellent
properties and a process for easily obtaining the electrolytic
manganese dioxide .
The objects of the present invention can be attained
by the followings.
(1) A treated manganese ore for use in producing
manganese sulfate therefrom, said treated ore having a degree
of manganese dissolution of 98.0% by weight or higher based
on the manganese contained in the treated manganese ore when
dissolved in sulfuric acid.
(2) The treated manganese ore of (1) , which has a degree
of iron dissolution of 70% by weight or higher based on the
iron contained in the treated manganese ore when dissolved
in sulfuric acid.
(3) The treated manganese ore of (1) or (2), wherein
the ratio of the amount of potassium soluble in sulfuric acid
to that of manganese contained in the treated manganese ore
(K/Mn) by weight is 0.001 or lower.
(4) The treated manganese ore of any one of (1) to
(3), which is one obtained by bringing a manganese ore into
Contact with a reducing gas at a temperature of from 400 to
790°C.
(5) A treatedlnanganese ore obtained by immersing the
treated manganese ore of (4) in water having a temperature
of from 70°C to the boiling point thereof as measured at
atmospheric pressure.
(6) The treated manganese ore of any one of (1) to
(5), which has a particle size of 500 pm or smaller.
(7) A process for producing the treated manganese ore
of any one of (1) to (6) , which comprises bringing a manganese
ore into contacted with a reducing gas at a temperature of
from 400 to 790°C to obtain a reduced ore.
(8) The process for producing a treated manganese ore
of (7) , wherein the manganese ore is pulverized to a particle
size of 500 pm or smaller before the reduced ore is obtained
therefrom.
(9) The process for producing a treated manganese ore
of (7) or (8), wherein the manganese ore is kept in contact
with the reducing gas at a temperature of from 400 to 790°C
for a period not shorter than the reduction saturation time.
(10) The process for producing a treated manganese
ore of any one of (7) to (9), wherein the reduced.ore obtained
is immersed in water having a temperature of from 70°C to the
boiling point thereof as measured at atmospheric pressure.
(11) The process for producing a treated manganese
ore of (10), wherein the reduced ore obtained is immersed in
water having a temperature of from 70°C to the boiling point
thereof as measured at atmospheric pressure, and washed.
(12) The process for producing a treated manganese
ore of (10), wherein the reduced ore obtained is immersed in
water having a temperature of from 70°C to the boiling point
thereofasmeasuredatatmosphericpressure,washedandfiltered.
(13) The process for producing a treated manganese
ore of any one of (7) to (12) , wherein the reducing gas comprises
p
Jneormoremembersselectedfromthegroupconsistingofhydrogen,
carbonmonoxide,sulfurdioxide,hydrogensulfide,andmethane.
(14) The process for producing a treated manganese
ore of any one of (7) to (13), wherein the reducing gas is
used in an amount of from 1.0 to 2.0 times the theoretical
amount thereof necessary for the reduction of the manganese
ore.
(15) The process for producing a treated manganese
ore of any one of (7) to (14), wherein the reducing gas is
one obtained by diluting said reducing gas with an inert gas.
(16) The process for producing a treated manganese
ore of any one of (7) to (15), wherein the time period of the
contact of the reducing gas with the manganese ore is from
to 120 minutes.
(17) The process for producing a treated manganese
ore of any one of (7) to (16) , wherein the Contact of the reducing
gas with the manganese ore is conducted continuously with a
rotary kiln.
(18) The process for producing a treated manganese
oreof(17),whereintherotarykilnhasacylindricalorprismatic
shape.
(19) The process for producing a treated manganese
ore of (17) or (18), wherein the rotary kiln is equipped with
a device for mixing the ore with the reducing gas.
(20) The process for producing a treated manganese
ore of (19), wherein the device for mixing the ore with the
reducing gas comprises one or more movable stirring blades
installed in the kiln or one or more stirring blades fixed
to the inner wall of the kiln.
(21) The process for producing a treated manganese
ore of any one of (7) to (20), which is conducted.continuously.
(22) The process for producing a treated manganese
ore of any one of (7) to (21) , wherein the reduced ore is cooled
in a nonoxidizing atmosphere and then immersed in water.
(23) The process for producing a treated manganese
ore of any one of (10) to (21), wherein the reduced ore is
immersed in water and then cooled in a nonoxidizing atmosphere .
(24) The process for producing a treated manganese
ore of (22) or (23), wherein the cooling is conducted
continuously.
(25) The process for producing a treated manganese
ore of any one of (7) to (24), wherein the immersion of the
reduced ore in water is conducted so as to yield a slurry in
which the concentration of the reduced ore is from 10 to 40%
by weight.
(26) The process for producing a treated manganese
ore of any one of (7) to (25), wherein the immersion of the
reduced ore in water is conducted for a period of from 1 to
hours.
(27) The process for producing a treated manganese
ore of any one of (7) to (26), wherein the immersion of the
reduced ore in water is<:onducted.in one or more stirring tanks
for continuous processing.
(28) Electrolytic manganese dioxide for use in
batteries which is obtained by dissolving the treated manganese
ore of any one of (l) to (6) in sulfuric acid, purifying the
resultant solution, and electrolytically oxidizing the
resultant manganese sulfate.
(29) A process for producing electrolytic manganese
dioxide which comprises adding sulfuric acid to the treated
manganese ore of any one of (1) to (6) to dissolve the ore
and thereby obtain an aqueous solution of manganese sulfate,
purifying the resultant aqueous solution of manganese sulfate,
and then subjecting the solution to electrolytic oxidation
to oxidize the manganese sulfate.
(30) A process for producing electrolytic manganese
dioxide which comprises obtaining a treated manganese ore by
the process of any one of (7) to (27), adding sulfuric acid
to the treated manganese ore to dissolve the ore and thereby
obtain an aqueous solution of manganese sulfate, purifying
the resultant aqueous solution of manganese sulfate, and then
subjecting the solution to electrolytic oxidation to oxidize
the manganese sulfate.
DETAILED DESCRIPTION OF THE INVENTION
The invention will be explained below in detail.
Anaturally occurring manganese ore is used as a starting
material for the treated manganese ore of the invention.
Manganese ores usually contain from 20 to 60% by weight manganese
and from 1 to 15% by weight iron . Preferred of these are manganese
oxide ores such as, e.g. , pyrolusite and psilomelane because
they are mined in large quantities , have a high manganese content ,
and are easily available.
It is essential that the treated manganese ore of the
invention have a degree of manganese dissolution in sulfuric
acid of 98 . 0% by weight or higher based on the manganese contained
in the treated manganese ore, which is exceedingly high in
view of the fact that the treated manganese ores obtained by
conventional techniques have a degree of manganese dissolution
in sulfuric acid lower than 98 . 0% by weight based on the manganese
contained in the treated manganese ore despite the treatment
in which the manganese ore is reduced to MnO (manganese monooxide)
through long-term heating at a high temperature.
The treated manganese ore of the invention, which is
obtained by treating a manganese ore, has a degree of manganese
dissolution in sulfuric acid as exceedingly high as 98.0% by
weight or above based on the manganese contained in the treated
manganese ore. This excellent property not only enables the
manganese to be industrially utilized more effectively but
also significantly reduces the amount of slag generation.
Because of this, the treated manganese ore of the invention
is exceedingly useful from the standpoints of industrial
production of manganese sulfate and environmental preservation.
The term "sulfuric acid" as used herein means a general
term for aqueous solutions containing sulfuric acid. Examples
thereof include concentrated sulfuric acid, diluted sulfuric
acid, and aqueous sulfuric acid solutions containing manganese
sulfate.
The degree of dissolution in sulfuric acid of the iron
contained in the treated manganese ore of the invention is
preferably 70% by weight or higher, more preferably 80% by
weight or higher, based on the iron contained in the treated
manganese ore. Such a high degree of iron dissolution is
effective in further reducing the amount of slag generation.
Furthermore, the potassium contained in the treated
manganese ore of the invention can be easily removed by immersing
the treated ore in water having a temperature of from 70°C
to the boiling point thereof as measured at atmospheric pressure .-
Hereinafter, this treated ore obtained by immersing the treated
manganese ore in water having a temperature of from 70°C to
the boiling point thereof as measured at atmospheric pressure
will be often referred to as "immersion—treated manganese ore" .
However, in this specification, there are cases where this
immersion—treated manganese ore is referred to as a treated
manganese ore like the treated ore obtained by reducing a
manganese ore;
This immersion—treated manganese ore is preferably
one in which the ratio of the amount of potassium soluble in
sulfuric acid to that of manganese contained in the treated
manganese ore (K/Mn) by weightais 0.001‘ or'lower.'
By‘ thus’ ‘ ‘ "
reducing the potassium content, manganese sulfate having an
exceedingly low potassium content can be produced from the
treated manganese ore of the invention. As a result, a
conventional operation for potassium removal can be omitted.
The particle size of the treated manganese ore of the
invention is preferably 500 pm or smaller, more preferably
300 pm or smaller, because the manganese and iron ingredients
contained in the treated ore particles of such a size can dissolve
in sulfuric acid -at an increased rate and this is effective
in the production of manganese sulfate. In addition, when
the treated ore obtained by reducing a manganese ore has a
particle size in that range , the efficiency of potassium removal
therefrom by warm-water immersion can also be improved. The
reason why the rate of dissolution in sulfuric acid is related
to the particle size of the treated manganese ore may be that
the dissolution depends on the surface area of the treated
manganese ore. If the particle size thereof is larger than
500 pm, the treated manganese ore has a reduced surface area
per unit amount thereof. This means that the treated manganese
ore has a smaller Contact area in dissolution in sulfuric acid.
Consequently, there are cases where the treated manganese
ore having such a large particle size has reduced solubility
and shows a lowered rate of dissolution in sulfuric acid.
The process of the invention for producing the treated
manganese ore will be described next.
This process comprises bringing a manganese ore as
a starting material into contact with a reducing gas at a
temperature of preferably from 400 to 790°C, more preferably
from 630 to 720°C, to obtain a reduced ore (hereinafter, this
step is referred to as "reduction step") , and optionally further
comprises immersing the reduced ore in water having a temperature
of from 70°C to the boiling point thereof as measured at
atmospheric pressure (hereinafter, this step is referred to
as "immersion step").
The manganese ore used as a starting material in the
process of the invention is preferably pulverized to a particle
size of 500 pm or smaller, desirably 300 pm or smaller, before
being subjected to the reduction step. This pulverization
treatment increases the surface area of the manganese ore.
As a result, the manganese ore can have an improved rate of
reduction and an improved rate of potassium dissolution in
producing the treated manganese ore of the invention . Although
methods for the pulverization treatment are not particularly
limited, preferred examples thereof include pulverization with
a pulverizer such as a mill or crusher. If the manganese ore
pulverized has a particle size larger than 500 pm, there are
cases where the manganese ore has a reduced rate of reduction
in the reduction step and where the treated manganese ore to
be obtained therefrom will have a reduced rate of manganese
dissolution when dissolved in sulfuric acid.
Methods for conducting the reduction step are not
particularly limited. However, in a preferred method for the
reduction step, the manganese ore as a starting material is
continuously brought into contact with,a,r.educing gas with.
heating and mixing by means of an external—heating type rotary
kiln to thereby accomplish the reduction.
In the case of using a rotary kiln, the reducing gas
and the raw manganese ore may be passed in the rotary kiln
in either the cocurrent or the countercurrent directions.
However,countercurrentcontactispreferredfromthestandpoint
of heightening the efficiency of contact between the reducing
gas and the ore to thereby obtain a higher degree of reduction
in_a shorter time period.
The rotary kiln is not particularly limited in shape
as long as the ore residing therein can be efficiently stirred.
However, the kiln desirably has a cylindrical or prismatic
shape.
The term "cylindrical shape” means a shape whose two
end faces are cricle-
The term "prismatic shape" means a shape whose two
endfacesarepolygonal,e.g.,pentagonal,hexagonal,heptagonal,
orioctagonal.
The rotary kiln more preferably is equipped inside
with a device for mixing the ore with a reducing gas so as
to heighten the efficiency of Contact between the ore and the
reducing gas.
Although the device forlmixing the ore withzireducing
gas is not particularly limited as long as it has the function
of mixing the ore with the reducing gas, it is preferred to
dispose a mixing device which has a simple structure, can be
maintainedeasily,andattainsanexcellentefficiencyofcontact.
Examples thereof include one or more movable stirring blades
installed in the rotary kiln and one or more stirring blades
fixed to the inner wall of the kiln, i .e. , the so-called lifter.
A rotary kiln equipped with those mixing devices in
combination may also be used.
Shapes of movable stirring blades and methods of the
use thereof are described in detail in, e.g., Japanese Patent
52177,JP-B—2—46877,JP-B55708,JP—B—2-55709,JP—B—2-55710,
and JP—B19471. The techniques shown in these prior art
references can be advantageously used in the invention.
By using a rotary kiln having a shape suitable for
efficiently stirring the ore residing therein as described
above and/or a rotary kiln equipped with a device for mixing
the ore with a reducing gas as described above, the reduction
of a manganese ore according to the invention can be carried
out in a shorter time period at a lower temperature with a
reducing—gas amount closer to the equivalent amount.
Thenumberofstirringbladesisnotparticularlylimited.
However, the number of movable stirring blades is preferably
3 or larger and that of stirring blades fixed to the inner
wall of the kiln is preferably 2 or larger,. from the standpoint
of heightening the efficiency of‘contact_
The reduction temperature in the reduction step is
preferably in the range of from 400 to 790°C, more preferably
in the range of from 630 to 720°C. The reasons for this are
as follows. If the reduction temperature is lower than 400°C,
there are cases where the raw’ manganese ore .is .reduced
insufficiently to give a treated manganese ore which has an
impaired degree of manganese dissolution when dissolved in
sulfuric acid. On the other hand, temperatures higher than
790°C may result in an impaired degree of manganese dissolution,
making it impossible to attain a degree of manganese dissolution
as high as 98.0% by weight or above based on the manganese
contained in the treated manganese ore.
Furthermore, the conventional reduction of a manganese
ore has necessitated use of a castable refractory material
or heat—resistant tungsten steel as the material of the oven
because the conventional reduction treatment is conducted at
a temperature as high as from 800 to l,00O°C. Namely, highly
expensive reducing ovens have been necessary. In contrast,
in the reduction in the process of the invention, ordinary
stainless steel can be used as an oven material and, hence,
the apparatus can be produced easily at low cost.
The reducing gas to be used in the reduction step can
be a gas having reducing properties, such as, e.g. , hydrogen,
carbon monoxide, sulfur dioxide, hydrogen sulfide, or methane.
These gases can be used not only alone but in any combination
of two or more thereof. Preferred of these is hydrogen mainly
because it has a high reaction rate and because the reaction
product gas yielded therefrom is water vapor, which does not
necessitate waste gas treatment;
The amount of the reducing gas to be used is preferably
at least 1.0 time the theoretical amount thereof necessary
for the reduction of the raw manganese.ore sofas to (complete
the reduction reactions to yield a treated manganese ore
retaining a high degree of manganese dissolution. When
profitability also is taken in account, the amount thereof
is preferably from 1.0 to 2.0 times the theoretical amount.
The term "theoretical amount of a reducing gas necessary
for the reduction of a manganese ore" as used herein means
the volumetric amount (liter) of the reducing gas necessary
for reducing the higher—order manganese oxide and higher—order
iron oxide contained in the manganese ore into MnO (manganese
monooxide) and FeO (iron monooxide) . In the case of an ore
containing manganese as manganese dioxide and iron as ferric
oxide, the theoretical amount of a reducing gas can be calculated
using the following equation:
W = W1 x (W2 x 0.01/55 + W3 x 0.01 X 0.5/56) x 0.082 x T/P
(whereinWis the volumetric amount (unit: liter) of the reducing
gas theoretically necessary for reducing the manganese ore;
W1 is the amount (unit: g) of the manganese ore to be reduced;
W2 is the manganese content (unit: wt%) in the manganese ore;
W3 is the iron content (unit: wt%) in the manganese ore; T
is the absolute temperature (unit: -K) of the reducing gas;
and P is the pressure (unit: atm) of the reducing gas).
The reducing gas to be used may be suitably diluted
with an inert gas such as, e_g. , nitrogen, argon, water vapor,
carbon dioxide, helium, or neon. Preferred of these is nitrogen
because it can be available in large quantities, can be handled
easily , and is inexpensive. Use of such an inert gas is effective
in lessening the dangers of the. reducing gas, e.g.(, explosion, l.
and in controlling the reactivity of the raw manganese ore
with the reducing gas.
The time period of keeping the manganese ore in contact
with a reducing gas in the reduction step is preferably not
shorter than the period in which the manganese ore can be
sufficiently reduced, i.e., the reduction saturation time,
and is more preferably 20 minutes or longer . The term "reduction
saturation time" as used herein means the period required for
the manganese ore to be sufficiently reduced by a reducing
gas. Whether the reduction has proceeded sufficiently can
be grasped, for example, by utilizing as an index thereto the
degree of dissolution of the iron contained in the ore in sulfuric
acid. When the degree of iron dissolution in sulfuric acid
has reached 70% by weight. or higher, preferably 80% by weight
or higher based on the iron contained in the treated manganese
ore, the manganese ore can be judged to have been sufficiently
reduced. Although the reduction saturation time varies
depending on the particle size and amount of the manganese
ore, amount of the reducing gas, reduction -temperature, etc. ,
it is about 30 minutes or longer at a reduction temperature
of, e . g . , 700°C . Reduction temperatures lower than 700°C result
in longer reduction saturation times, while reduction
temperatures higher than that result in shorter reduction
saturation times. By regulating the reduction period to a
given time period or longer, the manganese contained in the
manganese ore can be sufficiently reduced to finally give a
treated manganese «ore having a stably--high 'degreeIof~marnganese ~
dissolution in sulfuric acid. The especially preferred range
of the reduction period is from 20 to 120 minutes because even
when a reduction period longer than 120 minutes is used, not
only the degrees of dissolution of manganese and iron do not
increase any more but also the reduction uneconomically
necessitates an apparatus of a larger size.
After the reduction step, the reduced ore obtained
by the reduction step is preferably cooled to 150°C or lower
in a nonoxidizing atmosphere. This is because the manganese
ore immediately after completion of the reduction has a
temperature of several hundred degrees and is hence so unstable
that it may yield acid—insoluble matters upon exposure to air.
Since the rates of reactions for yielding acid—insoluble matters
are low at temperatures of 150°C or lower, the reduced ore
cooled to such a temperature may be subjected to the immersion
step. However, it is preferred to cool the reduced ore to
room temperature.
Those reactions proceed extremely quickly. It is
therefore preferred not only to prevent air inclusion during
the cooling but also to pass any of the inert gases and reducing
gases mentioned above or a mixture of two or more thereof through
the apparatus to more effectively inhibit the generation of
acid—insoluble matters.
A preferred method for the cooling is to use a rotary
kiln type cooling tube to continuously cool the reduced ore
while passing any of the aforementioned reducing gases and
inert gases. Although an air—cooled cooling tube may be used,
it is preferred to use a water—cooled cooling tube , for example ,
of the type in which the outer wall is showered with water,
from the standpoint of heightening the efficiency of cooling
to rapidly cool the reduced ore.
After the reduction step described above, at treatment
for immersing the reduced ore in water, i.e., an immersion
step , may be optionally conducted in order to immerse and dissolve
the potassium contained in the treated manganese ore. This
immersion step is accomplishedby immersing the reducedmanganese
ore obtained in the reduction step in water, i.e. , warm water,
heated to a temperature of from 70°C to the boiling point thereof
as measured at atmospheric pressure.
Methods for conducting the immersion step are not
particularly limited. However, in a preferred method for
accomplishing the step , one or more stirring tanks for continuous
processing are used to continuously stir and mix the reduced
manganese ore obtained in the reduction step with warm water
and the resultant slurry is continuously discharged therefrom.
The warm water to be used in the immersion step is
not particularly limited as long as it is heated water . Examples
thereof include pure water, ion—exchanged water, tap water,
and river water from which impurities have been removed.
Preferred of these are ion—exchanged water and the river water.
The temperature of the warm water is preferably not
lower than 70°C and not higher than the boiling point thereof
as measured at atmospheric pressure, and is more preferably
in the range of from 80 to 95°C. If the water temperature is
lower than 70°C , the solubilization ofpotassium is insufficient.
On the other hand, even when hot water having a temperature
exceeding the boiling point thereof as measured at atmospheric
pressure is used, the efficiency of potassium solubilization
cannot be expected to be significantly improved. In addition,
use of such hot water makes the process uneconomical because
it necessitates a pressure apparatus.
The treatment period in the immersion step is preferably
from 1 to 24 hours, more preferably from 3 to 5 hours. The
reasons for this are as follows. If the treatment period is
shorter than 1 hour, the solubilization of potassium may be
insufficient. On the other hand, even when the treatment period
exceeds 24 hours , the degree of potassium solubilization cannot
be heightened any more. In addition, such too long treatment
periods may necessitate a larger apparatus to impair
profitability.
The concentration of the reduced manganese ore in the
slurry obtained by adding warm water in the immersion step,
i.e., the slurry concentration, is preferably in‘the range
of from 10 to 40% by weight, more preferably from 20 to 30%
by weight. If the slurry concentration exceeds 40% by weight,
there are cases where the mixing of the reduced manganese ore
with the warm water becomes poor, resulting ininsufficient
potassium solubilization. On the other hand, even when the
slurry concentration is lower than 10% by weight, the efficiency
of potassium solubilization cannot be heightened any more.
In addition, such low slurry concentrations may necessitate
a large amount of water and a larger apparatus to impair
profitability.
After completion of the immersion step, the treated
manganese ore obtained is desirably washed in order to heighten
reproducibility and operating efficiency and remove impurities
like as a potassium. Water is usually used for the washing.
Examples thereof include pure water, ion—exchanged water, tap
water, and river water from which impurities have been removed.
Preferred of these are ion—exchanged water and the river water.
The washing water is used desirably in an amount of from 1
to 10 times by volume the amount of the cake of the treated
manganese ore. Although the number of washing operations is
not particularly limited, it is desirably from 1 to 10.
After the washing, the slurry may be directly subjected
to dissolution in an acid. It is, however, desirable from
the standpoint of water balance that the slurry be separated
by sedimentation or filtered by means of a filter press,
centrifugal separation, belt filter, etc. and the resultant
cake be subjected to dissolution’ in an acid. This slurry can’
be easily separated into the solid and the liquid, so that
the treated manganese ore can be easily separated by an ordinary
technique for solid/liquid separation.
In the invention, the steps and operations described
above can be carried out either batchwise or continuously.
However, they are preferably conducted in a continuous manner
capable of realizing a compacter equipment, improvement in
operation efficiency, and improvement in productivity. Methods
for continuous operations are suitably selected according to
the starting material, scale of production, etc. These steps
may be mutually combined organically. Furthermore, use may
be made of a method in which a treated product obtained in
one step is stored and thereafter subjected to the next step
either alone or together with treated products successively
obtained in that step.
The process of the invention for producing a treated
manganeseorecanbecarriedouteasily,safely,andefficiently
at low cost without using any special apparatus or expensive
chemical. The process is hence industrially useful.
Furthermore, the removal of potassium by immersion treatment
with warm water is effective in removing at least 80% of the
sodium, which is in the same group as potassium, contained
in the raw manganese ore.
Conventional methods for removing potassium from a
reducedorearehighlycostlyandnecessitateaspecialapparatus
and much labor because an expensive alkali is used to heat-treat
the ore or an expensive pressure apparatus such as, e.g , an
autoclave is used to treat the ore with hot water having a
temperature of 100°C or higher. These conventional methods
havehencebeendifficulttopracticeindustriallyz Incontrast,
the treated ore obtained by treating a reduced manganese ore
through immersion.in warntwater by the process of the invention
has high storage stability and is less apt to yield an
acid—insoluble matter. Although the reasons for this are
uncertain,itispresumedthatparticlesofthetreatedmanganese
ore are covered with a film of water and this water film inhibits
the formation of an acid—insoluble matter.
However, this presumption should not be construed as
limiting the scope of the invention in any way.
The treated manganese ore of the invention can be
obtained by the process described above.
As compared with conventional treated manganese ores,
the treated manganese ore of the invention is exceedingly reduced
in the amount of slag generation since the manganese and iron
contained therein have a high degree of dissolution in sulfuric
acid. Because of this, in the case where the treated manganese
ore of the invention is used as, e.g., a starting material
in producing electrolytic manganese dioxide for use as a
dry-battery material, the manganese dioxide can be efficiently
produced while attaining a reduced loss, etc.
Consequently, the treatedmanganese ore of the invention
is useful also as a starting material for manganese dioxide
to be used in primary batteries and secondary batteries. In
this application, the treated manganese ore of the invention
can be used in the following manner. The treated manganese
ore is added as a starting material to sulfuric acid, e.g. ,
dilute sulfuric acid, and dissolved therein to thereby produce
a solution of manganese sulfate. The resultant aqueous solution
of manganese sulfate is treated in an ordinary manner to remove
impurities such as iron and heavy metals therefrom. This
purified solution is subjected to electrolytic oxidation to
oxidize the manganese sulfate.’ Thus,,electrolytic manganese
dioxide can be produced.
The production of manganese dioxide from the treated
manganese ore of the invention has the following advantages.
Since the manganese and iron contained in the treated manganese
ore have a high degree of dissolution in sulfuric acid, the
amount of slag generation is exceedingly small as compared
with manganese dioxide production from conventional manganese
ores, leading to environmental preservation. Furthermore,
an aqueous manganese sulfate solution and electrolytic manganese
dioxide can be efficiently produced without causing a loss
of manganese from the starting material.
In addition, since the treated ore obtained by reducing
a manganese ore and treating the resultant reduced ore by
immersion in water having a temperature not higher than the
boiling point thereof as measured at atmospheric pressure has
an exceedingly low potassium content, a conventional operation
for potassium removal by an ordinary method can be omitted
in obtaining an aqueous manganese sulfate solution for use
in producing electrolytic manganese dioxide therefrom. Thus,
an aqueous manganese sulfate solution and electrolyticmanganese
dioxide can be produced efficiently, leading to the effective
utilization of resources.
The invention will be explained below in more detail
by reference to Examples, but the invention should not be
construed as being limited to these Examples. The contents
of manganese, iron, and potassium were determined in terms
of the weights of the atoms of therespectiveelements, contained. \
._.28_
in the manganese ingredients, iron ingredients, and potassium
ingredients.
EXAMPLE 1
A manganese dioxide ore containing 52.15% by weight
manganese and 2 . 63% by weight iron was pulverized to a particle
size of 300 pm or smaller. The pulverized ore was introduced
into an external-heating type rotary kiln having an inner
diameter of 200 mm and a length of 4 In at a rate of 1,100 g/min
and, simultaneously therewith, hydrogen gas diluted with
nitrogen to a hydrogen concentration of 40% by volume was
introduced into the same kiln in an amount of 1.2 times the
equivalent amount for reduction reaction so as to
countercurrently contact the ore with the gas . Thus , reducing
roasting was conducted. The reduction temperature and
reduction period were set at 650°C and 90 minutes , respectively.
The reduced ore obtained was cooled to 50°C or lower in a nitrogen
gas stream to obtain a reduced manganese ore having a manganese
content of 64.30% by weight and an iron content of 2.91% by
weight. The treated manganese ore obtained was analyzed by
screening with sieves. As a result, the particle size thereof
was found to be 300 pm or smaller.
This treated manganese ore was dissolved in 3.0% by
weight sulfuric acid heated to 90°-C in such an amount as to
result in a pH of 1.5. Thevresultant mixture was separated
by filtration into a manganese sulfate solution and a slag.
As a result, the amount of the slag on a dry basis was 0.06
kg per kg of the.raw manganese ore. Analysis of this slag
by an ordinary method revealed that when the treated manganese
ore obtained was dissolved in the dilute sulfuric acid, a degree
of manganese dissolution was 99.9% by weight based on the
manganese contained in the raw manganese ore and a degree of
iron dissolution was 89 . 9% by weight based on the iron contained
in the raw manganese ore.
COMPARATIVE EXAMPLE 1
A manganese dioxide ore containing 52.15% by weight
manganese and 2 . 63% by weight iron was pulverized to a particle
size of 300 pm or smaller. The pulverized ore was introduced
into an external-heating type rotary kiln having an inner
diameter of 200 mm and a length of 4 m at a rate of 1,100 g/min
and, simultaneously therewith, CO gas diluted with nitrogen
to a CO concentration of 40% by volume was introduced into
the same kiln in an amount of 1.2 times the equivalent amount
for reduction reaction so as to countercurrently contact the
ore with the gas . Thus, reducing roasting was conducted. The
reduction temperature and reduction period were set at l,OOO°C
and 120 minutes, respectively. The reduced ore obtained was
cooled to room temperature in a. nitrogen gas stream to obtain
a treated manganese ore having a manganese content of 62.96%
by weight and an iron content of 4 . 04% by weight. The treated
manganese ore obtained was analized by screening with sieves.
As a result, the particle size thereof was found to be 300
pm or smaller.
This treated manganese ore was dissolved in 3.0% by
weight sulfuric, acid heated to 9_0‘?_C. .in . such .an ‘amount \ as ‘to
result in a pH of 1.5. The resultant mixture was separated
by filtration into a manganese sulfate solution and a slag.
As a result, the amount of the slag on a dry basis was 0.14
kg per kg of the raw manganese ore. Analysis of this slag
by an ordinary method revealed that when the treated manganese
ore obtained was dissolved in the dilute sulfuric acid, a degree
of manganese dissolution was 95 .4% by weight based on the
manganese contained in the raw manganese ore and a degree of
iron dissolution was 42 . 3% by weight based on the iron contained
in the raw manganese ore.
A comparison between Example 1 and Comparative Example
1 given above shows that the manganese ore in Example 1 was
reduced more sufficiently than in Comparative Example 1, so
that the treated manganese ore obtained in Example 1 had higher
degrees of manganese dissolution and iron dissolution in dilute
sulfuric acid.
EXAMPLE 2
A manganese dioxide ore containing 52 .295 by weight
manganese , 2 . 63% by weight iron, and 5 , 750 ppm (0 . 575% by weight)
potassium was pulverized to a particle size of 300 pm or smaller.
The pulverized ore was introduced into an external—heating
type rotary kiln having an inner diameter of 200 mm and a length
of 4 In at a rate of 1,100 g/min and, simultaneously therewith,
hydrogen gas diluted with nitrogen to a hydrogen concentration
of 40% by volume was introduced into the same kiln in an amount
of 1.2 times the equivalent amount for reduction reaction so
as to countercurrently Contact the ore with -the——gas. Thus, -V
reducing roasting was conducted. The reduction temperature
and reduction period were set at 700°C and 30 minutes,
respectively. The resultant reduced ore was cooled to 50°C
or lower in a nitrogen gas stream and then introduced into
a stirring tank, in which the reduced ore was treated with
90°C warm water for 5 hours at a slurry concentration of 20%
by weight. The ore was then washed and recovered by filtration
to obtain a treated manganese ore according to the invention
for manganese sulfate production, which had a manganese content
of 37 . 4% by weight, iron content of 1 . 71% by weight, andpotassium
content of 279 ppm (0 . 0279% by weight) . This treated manganese
ore was analyzed by wet screening with sieves. As a result,
the particle size thereof was found to be 300 pm or smaller.
In 3 . 0% by weight aqueous sulfuric acid solution heated
to 90°C was dissolved 13.3 g of the treated manganese ore so
as to result in a pH of 1.5. This mixture was separated by
filtration into a manganese sulfate solution and a slag. The
resultant sulfuric acid solution had a manganese content of
1.35% by weight, iron content of 486 ppm (0.0486% by weight) ,
and potassium content of 6 ppm (0.000006% by weight). The
slag weighed 0.48 g and had a manganese content of 0.69% by
weight, iron content of 10.9% by weight, and potassium content
of 2 ,46O ppm. These results show that the degree of manganese
dissolution when the treatedmanganese ore obtained was dissolved
in the sulfuric acid (hereinafter referred to simply as "degree
of manganese dissolution") was 99.9% by weight based on the
manganese contained in the raw manganese ore and the degree
of iron dissolution when the treated manganese ore obtained
was dissolved in the sulfuric acid (hereinafter referred to
simply as "degree of iron dissolution") was 76.8% by weight
based on the iron contained in the raw'manganese ore, and that
the ratio of the amount of potassium soluble in sulfuric acid
to that of manganese contained in the treated manganese ore
by weight (hereinafter referred to as "K/Mn") was 0.000507.
The results obtained are shown in Table 1.
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Furthermore, sulfuric acid was added to the treated
manganese ore. The ore was dissolved in the acid to obtain
a manganese sulfate solution. An aqueous hydrogen peroxide
solution was added to the aqueous manganese sulfate solution,
and the resultant mixture was neutralized with milk of lime.
After the solid was removed by filtration, the residual
manganese sulfate solution. was subjected. to electrolytic
oxidation at a temperature of 90°C and a current density of
1.0 A/dmz. Thus, high-purity electrolytic manganese dioxide
for use in batteries was obtained.
EXAMPLE 3
A treated manganese ore was obtained in the same manner
as in Example 2, except that the reduction period was set at
90 minutes. This treated.manganese ore for manganese sulfate
production was analyzed by wet screening with sieves. As a
result, the particle size thereof was found to be 300 pm or
smaller.
.1 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
EXAMPLE 4
A treated manganese ore was obtained in the same manner
as in Example 2, except that the reduction period was set at
90minutesandtheperimdofthewarm-watertreatmentwaschanged
to 3 hours. This treated.manganese ore for manganese sulfate
production was analyzed by wet screening withisieves. As a
result, the particle size thereof was found to be 300 pm or
smaller.
.3 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
EXAMPLE 5
A treated manganese ore was obtained in the same manner
as in Example 2, except that hydrogen gas diluted with nitrogen
to a hydrogen concentration of 20% by volume was used in an
amountof2.0timestheequivalentamountforreductionreaction,
that the reduction temperature and reduction period were set
at 710°C and 90 minutes, respectively, and that the slurry
concentration was changed to 40% by weight. This treated
manganese ore for manganese sulfate production was analyzed
by wet screening with sieves. As a result, the particle size
thereof was found to be 300 pm or smaller.
.1 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
EXAMPLE 6
A treated manganese ore was obtained in the same manner
as in Example 2, except that hydrogen gas diluted.with nitrogen
to a hydrogen concentration of 90% by volume was used in an
amountof1_6timestheequivalentamountforreductionreaction,
that the reduction period was set,at 90 minutes, and that the
temperature of the warm water was changed to 80°C. This treated
manganese ore for manganese sulfate production was analyzed
by wet screening with sieves. As a result, the particle size
thereof was found to be 300 pm or smaller.
16.0 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
COMPARATIVE EXAMPLE 2
A treated manganese ore was obtained in the same manner
as in Example 2, except that the reduction temperature and
reduction period were set at 350°C and 60 minutes , respectively,
and that the temperature of the warm water was changed to 80°C.
This treated manganese ore for manganese sulfate production
was analyzed by wet screening with sieves. As a result, the
particle size thereof was found to be 300 um or smaller.
13.4 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
COMPARATIVE EXAMPLE 3
A treated manganese ore was obtained in the same manner
as in Example 2, except that CO gas was used as a reducing
gas, that the reduction temperature and reduction period were
set at l,O0O°C and 120 minutes, respectively, and that the
reduced ore was cooled to room temperature in a nitrogen gas
stream, subsequently introduced into an autoclave stirring«—
tank, and then treated therein with 110°C hot water. This treated
manganese ore for manganese sulfate production was analyzed
by wet screening with sieves. As a result, the particle size
thereof was found to be 300 pm or smaller.
.7 g of this treated manganese ore was treated in
the same manner as in Example 2 to determine the degree of
manganese dissolution, degree of iron dissolution, and K/Mn.
The results obtained are shown in Table 1.
The invention produces the following effects.
1) The treated manganese ore of the invention has an exceedingly
high degree of manganese dissolution when dissolved in sulfuric
acid, and this property makes the treated ore highly suitable
for use in obtaining a manganese sulfate solution for producing
electrolytic manganese dioxide therefrom. Furthermore, the
treated manganese ore is extremely reduced in the amount of
slag generation as compared with conventional reduced manganese
ores. The treated manganese ore is hence extremely useful
in practical use.
2) When the treated manganese ore of the invention obtained
through a reduction treatment is treated with warm water, a
treated manganese ore having a reduced potassium content is
obtained. This treated manganese ore has properties which
make the treated ore highly suitable for use in obtaining a
high-purity manganese sulfate solution for producing
electrolytic manganese dioxide therefrom.
) The process of the invention for producing a treated manganese
ore necessitatesineither a reducing apparatus or pressure
.‘.:”x‘
apparatus made of an expensive material nor an expensive alkali .
By treating with warm water the treated.manganese ore of the
invention obtained through a reduction treatment, a treated
manganese ore can be obtained which gives a manganese sulfate
solution having an exceedingly reduced potassium concentration
and further having an exceedingly reduced concentration of
alkali metals such as sodium, which are in the same group as
potassium. Thus, a treatedqmanganese ore for use in.producing
high-qualitymanganesesulfatetherefromcanbeeasilyproduced.
Furthermore,theequipmentcostislow. Theprocessissuitable
for mass production and industrial use.
4) The process of the invention for producing electrolytic
manganesedioxideusesthetreatedmanganeseoreoftheinvention,
havinganextremelylowimpuritycontent,asastartingmaterial.
Consequently, the burden imposed on a step for impurity removal
canbelessenedandtheprocessisextremelyusefulindustrially.
Themanganesedioxideforbatteriesobtainedfromthatstarting
material is of high quality.
While the invention has been described.in detail and
with reference to specific embodiments thereof, it will be
apparent to one skilled in the art that various changes and
modifications can be made therein without departing from the
spirit and scope thereof.
Claims (34)
1. A treated manganese ore for use in producing manganese sulfate therefrom, said treated ore having a degree of manganese dissolution of 98.0% by weight or higher based on the manganese contained in the treated manganese ore when dissolved in sulfuric acid.
2. The treated manganese ore of claim 1, which has a degree of iron dissolution of 70% by weight or higher based ontheironcontainedinthetreatedmanganeseorewhendissolved in sulfuric acid.
3. The treated.manganese ore of claim 1 or 2, wherein the ratio of the amount of potassium soluble in sulfuric acid to that of manganese contained in the treated manganese ore (K/Mn) by weight is 0.001 or lower.
4. The treated manganese ore of any one of claims 1 to 3, which is one obtained by bringing a manganese ore into Contact with a reducing gas at a temperature of from 400 to 790°C.
5. A treated.manganese ore obtained.by immersing the treatedxnanganese ore of claim.4 in water having a temperature of from 70°C to the boiling point thereof as measured at atmospheric pressure.
6. The treated manganese ore of any one of claims 1 to 5, which has a particle size of 500 pm or smaller.
7. A.process for producing the treated.manganese ore of any one of claims 1 to 6, which comprises bringing a manganese ore into contacted with a reducing gas at a temperature of "\from 400 to 790°C to obtain a reduced ore.
8. The process for producing a treated manganese ore of claim 7 , wherein the manganese ore is pulverized to a particle size of 500 pm or smaller before the reduced ore is obtained therefrom.
9. The process for producing a treated manganese ore of claim 7 or 8, wherein the manganese ore is kept in contact with the reducing gas at a temperature of from 400 to 790°C for a period not shorter than the reduction saturation time.
10 . The process for producing a treated manganese ore of any one of claims 7 to 9, wherein the reduced ore obtained is immersed in water having a temperature of from 70°C to the boiling point thereof as measured at atmospheric pressure.
11. The process for producing a treated manganese ore of claim 10, wherein the reduced ore obtained is immersed in water having a temperature of from 70°C to the boiling point thereof as measured at atmospheric pressure, and washed.
12. The process for producing a treated manganese ore of claim 10, wherein the reduced ore obtained is immersed in water having a temperature of from 70°C to the boiling point thereof as measured at atmospheric pressure , washed and filtered.
13. The process for producing a treated manganese ore of any one of claims 7 to 12, wherein the reducing gas comprises one or more members selected from the group consisting of hydrogen , carbon monoxide, sulfur dioxide, hydrogen sulfide, andmethane.
14. The process for producing a treated manganese ore of any one of claims 7 to 13, wherein the reducing gas is used "Kin an amount of from 1.0 to 2.0 times the theoretical amount thereof necessary for the reduction of the manganese ore.
15. The process for producing a treated manganese ore of any one of claims 7 to 14, wherein the reducing gas is one obtained by diluting said reducing gas with an inert gas.
16. The process for producing a treated manganese ore of any one of claims 7 to 15, wherein the time period of the contact of the reducing gas with the manganese ore is from 20 to 120 minutes.
17 . The process for producing a treated manganese ore of any one of claims 7 to 16, wherein the contact of the reducing gas with the manganese ore is conducted continuously with a rotary kiln.
18. The process for producing a treated manganese ore of claim 17 , wherein the rotary kiln has a cylindrical or prismatic shape.
19 . The process for producing a treated manganese ore of claim 17 or 18, wherein the rotary kiln is equipped with a device for mixing the ore with the reducing gas.
20 . The process for producing a treated manganese ore of claim 19, wherein the device for mixing the ore with the reducing gas comprises one or more movable stirring blades installed in the kiln or one or more stirring blades fixed to the inner wall of the kiln.
21. The process for producing a treated manganese ore of any one of claims 7 to 20, which is conducted continuously.
22. The process for producing a treated manganese ore "X of any one of claims 7 to 21, wherein the reduced ore is cooled in a nonoxidizing atmosphere and then immersed in water.
23. The process for producing a treated manganese ore of any one of claims 10 to 21 , wherein the reduced ore is immersed in water and then cooled in a nonoxidizing atmosphere.
24 . The process for producing a treated manganese ore of claim 22 or 23, wherein the cooling is conducted continuously.
25 . The process for producing a treated manganese ore of any one of claims 7 to 24, wherein the immersion of the reduced ore in water is conducted so as to yield a slurry in which the concentration of the reduced ore is from 10 to 40% by weight.
26 . The process for producing a treated manganese ore of any one of claims 7 to 25, wherein the immersion of the reduced ore in water is conducted for a period of from 1 to 24 hours.
27 . The process for producing a treated manganese ore of any one of claims 7 to 26, wherein the immersion of the reduced ore in water is conducted in one or more stirring tanks for continuous processing.
2 8. Electrolytic manganese dioxide for use in batteries which is obtained by dissolving the treated manganese ore of any one of claims 1 to 6 in sulfuric acid, purifying the resultant oxidizing the resultant solution, and electrolytically manganese sulfate.
29. A process for producing electrolytic manganese dioxide which comprises adding sulfuric acid to the treated 10 ~manganese ore of any one of claims 1 to 6 to dissolve the ore and thereby obtain an aqueous solution of manganese sulfate, purifying the resultant.aqueous solution of1nanganese sulfate, and then subjecting the solution to electrolytic oxidation to oxidize the manganese sulfate.
30. A process for producing electrolytic manganese dioxide which comprises obtaining a treated manganese ore by the process of any one of claims 7 to 27, adding sulfuric acid to the treated manganese ore to dissolve the ore and thereby obtain an aqueous solution of manganese sulfate, purifying the resultant aqueous solution of manganese sulfate, and then subjecting the solution to electrolytic oxidation to oxidize the manganese sulfate. 10
31. A treated maganese ore for use in producing maganese sulfate therefrom as described herein with reference to and/or as exemplified in the accompanying examples.
32. A process for producing treated maganese ore as described herein with reference to and/or as exemplified in the accompanying examples.
33. Electrolytic manganese dioxide for use in batteries as described herein with reference to and/or as exemplified in the accompanying examples.
34. A process for producing electrolytic manganese dioxide as described herein with reference to and/or as exemplified in the accompanying examples. DJC2997 TOMKINS & CO . 45
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JPJAPAN04/04/20002000-106707 | |||
JP2000106707 | 2000-04-04 | ||
JP2000152754 | 2000-05-19 |
Publications (2)
Publication Number | Publication Date |
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IE20010338A1 IE20010338A1 (en) | 2002-12-11 |
IE84218B1 true IE84218B1 (en) | 2006-05-17 |
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