CA1109645A - Process for the production of battery-grade manganese dioxide - Google Patents
Process for the production of battery-grade manganese dioxideInfo
- Publication number
- CA1109645A CA1109645A CA339,079A CA339079A CA1109645A CA 1109645 A CA1109645 A CA 1109645A CA 339079 A CA339079 A CA 339079A CA 1109645 A CA1109645 A CA 1109645A
- Authority
- CA
- Canada
- Prior art keywords
- solution
- process according
- mno2
- precipitate
- mgo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 28
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 18
- 235000012254 magnesium hydroxide Nutrition 0.000 claims abstract description 18
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 4
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 4
- 239000011565 manganese chloride Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000000460 chlorine Substances 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract 6
- 238000001914 filtration Methods 0.000 description 10
- 235000002908 manganese Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960000816 magnesium hydroxide Drugs 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940075799 deep sea Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Process for the production of battery-grade manganese dioxide.
Abstract Battery-grade MnO2 is produced by (a) treating a MnCl2 solution with Cl2 and Mg(OH)2 whereby obtaining a MgCl2 solution that contains a MnO2 precipitate;
(b) allowing to digest the precipitate in the MgCl2 solution in presence of Cl2 under pressure;
(c) separating the digested precipitate from the solution; and (d) washing and drying the precipitate.
Owing to step (b), operating conditions in step (a) may be such that a concentrated MgCl2 solution is obtained, which is important for the further processing of that solu-tion by pyrohydrolysis.
Abstract Battery-grade MnO2 is produced by (a) treating a MnCl2 solution with Cl2 and Mg(OH)2 whereby obtaining a MgCl2 solution that contains a MnO2 precipitate;
(b) allowing to digest the precipitate in the MgCl2 solution in presence of Cl2 under pressure;
(c) separating the digested precipitate from the solution; and (d) washing and drying the precipitate.
Owing to step (b), operating conditions in step (a) may be such that a concentrated MgCl2 solution is obtained, which is important for the further processing of that solu-tion by pyrohydrolysis.
Description
The present invention relates to a process for the producti-on of battery-grade manganese dioxide from a manganese chloride solution, in which said solution is treated with chlorine, while maintaining the pH of the solution between 0.5 and 3 by adding MgO and/or Mg(OH)2, so as to precipitate most of the man-ganese thereby producing a MgC12 solution poor in manganese and containing a MnO2 precipitate, the MnO2 precipitate is separated from said MgC12 solution and the MnO2 precipitate is washed and dried. This process is based upon the following reactions:
MnC12 + C12 + 2 H20 > MnO2 + 4 HC1 4 HCl + 2 MgO ~ 2 MgC12 + 2 H20 MnC12 + C12 + 2 MgO )MnO2 + 2 MgC12 Such process has been described in the United States Patent No. 3,770,868. In this known process, operating conditions are such that said separated MgC12 solution contains 48 g/l of magnesium as a chloride.
It has been found by the applicant that the above defined process is difficult to realize when it is performed under such conditions that said separated MgC12 solution contains considerably more magnesium, namely from 85 to 130 g/l of magnesium as a chloride, because it results in a manganese dioxide precipitate with high magnesium content that has to be purified by an excessive washing.
However, in such a process it is desirable to produce a concentrated MgC12 solution, since this solution normally has to be pyrohydrolized to recover MgO and HCl. Pyrohydrolyzing a dilute solution requires evaporation of excessive quantities of water.
- The object of the present invention is to provide a process as defined above, which enables one to produce both a concentrated MgC12 solution and a MnO2 precipitate that does not require an ~excessive washing.
.
$~
It has been found that the aforesaid-serious drawback can be avoided in a surprisingly simple way by digestion of the MnO2 precipitate in the MgCl2 solution in presence of chlorine under pressure.
The process according to the present invention is thus essentially characterized in that the MnO2 precipitate is digested in the MgCl2 solution in presence of chlorine under pressure.
Digestion is preferably performed under a chlorine pressure of at least 2 kg/cm , or else the digestion time required for obtaining a precipitate of good quality would be excessively long.
Preferably, the precipitate is allowed to digest for at least l hour, or else the chlorine pressures required would be excessively high to obtain a precipitate of good quality.
In the process of the present invention the MnO2 precip-itation itself can be carried out under atmospheric pressure, as is done in the above mentioned process of the prior art; it is however much more advantageous to perform this precipitation in an autoclave under a chlorine pressure of between 1.5 and 4.5 kg/cm , since in the latter case, MnO2 precipitates much faster.
Further details and particulars of the process of the invention will appear from the description hearafter of a pre-ferred mode of performing the process of the invention, illustrated in the attached diagram and given as a non-restrictive example.
Solutions with 110 to 130 g/l of Mn as MnCl2 and 25 to 35 g/l of ~g as MgC12 are treated. Such solutions are e.g. produced after extraction of metals such as Ni, Co, Cu and Fe from liquors resulting from the leaching of manganiferous deepsea nodules, according to the process described in the United States Patent No.
4,026,773.
MnO2 precipitation is performed, under vi`gorous stirring, ~ ~ 3 ~, , S6~
in an autoclave under chlorine pressure of between 1.5 and 4.5 kg/cm and at a temperature of between 50 and 100C, preferably between 65 and 80C.
During the precipitation reaction, the pH of the solution is kept between 1 and 2.5 by adding a suspension of magnesium hydrox-ide in a magnesium chloride solution, the solution used for preparing that suspension containing 90 to 110 g/l of Mg as a chloride and the suspension itself containing 600 to 800 g, preferably 660 to 720 g of Mg(OH)2 per litre of solution.
The aforesaid precipitation reaction is carried on until a residual manganese content of between 10 to 20 g/l is reached in the solution, said content being reached after between 30 to 120 minutes, depending on the chlorine ~ressure and the pH.
When reaching said residual manganese content, no more magnesium hydroxide is added and the precipitate is allowed to digest in the solution depleted in manganese for a 2 to 4 h period, while maintaining the chlorine pressure in the autoclave hetween 2.5 and 6 kg/cm .
- After digestion in the autoclave, the MnO2 precipitate is separated from the solution depleted in manganese by filtration, the filtration cake is washed, the washed filtration cake is re-pulped in water, it is filtered again, the filtration cake is washed with water and dried at between 100 and 110C.
In this way MnO2 is obtained, which contains 100 to 300 ppm (parts per million) of magnesium and which is battery-grade.
MgO andjor Mg(OH)2 is added to the solution depleted in manganese, that contains besides iO to 20 g/l of manganese, 85 to 100 g/l of magnesium as a chloride, so as to precipitate the residual manganese as an hydroxide and to obtain a practicaliy manganese free MgC12 solution. The so o~tained precipitate is separated from the .
.'. ' '~.
' ` ; ~ ` ' ' ' 3~ 645 demanganized MgC12 solution. rart of this solution is used to prepare the.previously mentioned magnesium hydroxide suspension and the other part is subjected to a pyrohydrolysis so as to produce MgO, that is used to prepare the previously mentioned Mg(OH)2 suspension, and HCl.
- 4a -Example 1 _________ This example relates to the production of battery-grade MnO2 according to the above described preferred mode of carrying out the process of the invention.
The starting solution contains in g/l : 114 Mn, 34 Mg, 9 Na, 5 K, 8 Ca.
The operation is performed in an autoclave with stirrer on 25 l solution, at a temperature of 75C, under a 2 kg/cm2 chlorine pressure, the stirrer rotating at a speed of 350 rpm. The pH of the solution ls maintained at 2 by addlng Mg(OH)2 as a suspension in a MgCl2 solution containing 90 g Mg/l as a chloride (720 g Mg(OH)2 per litre of solution).
After 2 hours, the Mn content of the solution has dropped to 20 g/l while the Mg content of the solution has risen to 91 g/l. No more Mg(OH)2 is added and the reaction mixture is further stirred for 2 hours, while maintaining the chlorine pressure at 4 kg/cm .
After this digestion, the MnO2 precipitate is filtered, the filtration cake is once washed with 50 l of water, the washed cake is repulped in 25 l of water at 70C (200 g of cake per liter), it is filtered again and the filtration cake is once washed with 100 l of water. The cake is dried at 105C.
In this way MnO2 is obtained with the following properties, which proves that this MnO2 is battery-grade :
- Chemical analysis :
Mn 60.5 MnO2 > 89 %
H20 2 %
- . -, , :. ,.,. ,,:, , - -- . . - : . , . :. , Cu ~ 10 ppm Ni ~ 10 ppm Co~ 10 ppm -Mg~ 200 ppm Cl~ 200 ppm x value in MnO 1.94 ~ x S 1.96 - pH : 5.2 - Physical properties :
specific surface 50 m2/g (BET) crystal structure rho-gamma average particle size 4 microns (Coulter counter) average pore diameter 15 A
- Electrochemical properties :
1) Equilibrium potential in a saturated Na4Cl solution : + 780 mv (Standard Hydrogen Electrode)
MnC12 + C12 + 2 H20 > MnO2 + 4 HC1 4 HCl + 2 MgO ~ 2 MgC12 + 2 H20 MnC12 + C12 + 2 MgO )MnO2 + 2 MgC12 Such process has been described in the United States Patent No. 3,770,868. In this known process, operating conditions are such that said separated MgC12 solution contains 48 g/l of magnesium as a chloride.
It has been found by the applicant that the above defined process is difficult to realize when it is performed under such conditions that said separated MgC12 solution contains considerably more magnesium, namely from 85 to 130 g/l of magnesium as a chloride, because it results in a manganese dioxide precipitate with high magnesium content that has to be purified by an excessive washing.
However, in such a process it is desirable to produce a concentrated MgC12 solution, since this solution normally has to be pyrohydrolized to recover MgO and HCl. Pyrohydrolyzing a dilute solution requires evaporation of excessive quantities of water.
- The object of the present invention is to provide a process as defined above, which enables one to produce both a concentrated MgC12 solution and a MnO2 precipitate that does not require an ~excessive washing.
.
$~
It has been found that the aforesaid-serious drawback can be avoided in a surprisingly simple way by digestion of the MnO2 precipitate in the MgCl2 solution in presence of chlorine under pressure.
The process according to the present invention is thus essentially characterized in that the MnO2 precipitate is digested in the MgCl2 solution in presence of chlorine under pressure.
Digestion is preferably performed under a chlorine pressure of at least 2 kg/cm , or else the digestion time required for obtaining a precipitate of good quality would be excessively long.
Preferably, the precipitate is allowed to digest for at least l hour, or else the chlorine pressures required would be excessively high to obtain a precipitate of good quality.
In the process of the present invention the MnO2 precip-itation itself can be carried out under atmospheric pressure, as is done in the above mentioned process of the prior art; it is however much more advantageous to perform this precipitation in an autoclave under a chlorine pressure of between 1.5 and 4.5 kg/cm , since in the latter case, MnO2 precipitates much faster.
Further details and particulars of the process of the invention will appear from the description hearafter of a pre-ferred mode of performing the process of the invention, illustrated in the attached diagram and given as a non-restrictive example.
Solutions with 110 to 130 g/l of Mn as MnCl2 and 25 to 35 g/l of ~g as MgC12 are treated. Such solutions are e.g. produced after extraction of metals such as Ni, Co, Cu and Fe from liquors resulting from the leaching of manganiferous deepsea nodules, according to the process described in the United States Patent No.
4,026,773.
MnO2 precipitation is performed, under vi`gorous stirring, ~ ~ 3 ~, , S6~
in an autoclave under chlorine pressure of between 1.5 and 4.5 kg/cm and at a temperature of between 50 and 100C, preferably between 65 and 80C.
During the precipitation reaction, the pH of the solution is kept between 1 and 2.5 by adding a suspension of magnesium hydrox-ide in a magnesium chloride solution, the solution used for preparing that suspension containing 90 to 110 g/l of Mg as a chloride and the suspension itself containing 600 to 800 g, preferably 660 to 720 g of Mg(OH)2 per litre of solution.
The aforesaid precipitation reaction is carried on until a residual manganese content of between 10 to 20 g/l is reached in the solution, said content being reached after between 30 to 120 minutes, depending on the chlorine ~ressure and the pH.
When reaching said residual manganese content, no more magnesium hydroxide is added and the precipitate is allowed to digest in the solution depleted in manganese for a 2 to 4 h period, while maintaining the chlorine pressure in the autoclave hetween 2.5 and 6 kg/cm .
- After digestion in the autoclave, the MnO2 precipitate is separated from the solution depleted in manganese by filtration, the filtration cake is washed, the washed filtration cake is re-pulped in water, it is filtered again, the filtration cake is washed with water and dried at between 100 and 110C.
In this way MnO2 is obtained, which contains 100 to 300 ppm (parts per million) of magnesium and which is battery-grade.
MgO andjor Mg(OH)2 is added to the solution depleted in manganese, that contains besides iO to 20 g/l of manganese, 85 to 100 g/l of magnesium as a chloride, so as to precipitate the residual manganese as an hydroxide and to obtain a practicaliy manganese free MgC12 solution. The so o~tained precipitate is separated from the .
.'. ' '~.
' ` ; ~ ` ' ' ' 3~ 645 demanganized MgC12 solution. rart of this solution is used to prepare the.previously mentioned magnesium hydroxide suspension and the other part is subjected to a pyrohydrolysis so as to produce MgO, that is used to prepare the previously mentioned Mg(OH)2 suspension, and HCl.
- 4a -Example 1 _________ This example relates to the production of battery-grade MnO2 according to the above described preferred mode of carrying out the process of the invention.
The starting solution contains in g/l : 114 Mn, 34 Mg, 9 Na, 5 K, 8 Ca.
The operation is performed in an autoclave with stirrer on 25 l solution, at a temperature of 75C, under a 2 kg/cm2 chlorine pressure, the stirrer rotating at a speed of 350 rpm. The pH of the solution ls maintained at 2 by addlng Mg(OH)2 as a suspension in a MgCl2 solution containing 90 g Mg/l as a chloride (720 g Mg(OH)2 per litre of solution).
After 2 hours, the Mn content of the solution has dropped to 20 g/l while the Mg content of the solution has risen to 91 g/l. No more Mg(OH)2 is added and the reaction mixture is further stirred for 2 hours, while maintaining the chlorine pressure at 4 kg/cm .
After this digestion, the MnO2 precipitate is filtered, the filtration cake is once washed with 50 l of water, the washed cake is repulped in 25 l of water at 70C (200 g of cake per liter), it is filtered again and the filtration cake is once washed with 100 l of water. The cake is dried at 105C.
In this way MnO2 is obtained with the following properties, which proves that this MnO2 is battery-grade :
- Chemical analysis :
Mn 60.5 MnO2 > 89 %
H20 2 %
- . -, , :. ,.,. ,,:, , - -- . . - : . , . :. , Cu ~ 10 ppm Ni ~ 10 ppm Co~ 10 ppm -Mg~ 200 ppm Cl~ 200 ppm x value in MnO 1.94 ~ x S 1.96 - pH : 5.2 - Physical properties :
specific surface 50 m2/g (BET) crystal structure rho-gamma average particle size 4 microns (Coulter counter) average pore diameter 15 A
- Electrochemical properties :
1) Equilibrium potential in a saturated Na4Cl solution : + 780 mv (Standard Hydrogen Electrode)
2) Test of a R12-paper line type battery made of a mixture of 85 % of MnO2 and 15 % of acetylene black :
- discharge conditions : 5 minutes/hour during 10 hours/day on a 5 ohm resistance till the potential at the battery terminals drops to 0.9 V
- discharge time : 7 hours It is to be noted that in the same conditions a commercial battery grade MnO2 has given a discharge time of 6.5 hours.
Example 2 _________ The same mode of operation as in example 1 is used, but the MnO2 precipitate i6 not digested under chlorine pressure.
'' ~ ~ -' ' '- ' '; ~
s The MnO2 precipitate is thus immediately filtered as soon as no more Mg(OH)2 is added.
The filtration cake is processed in the same way as in example l and it is stated that the thus obtained MnO2 contains-e~ percent in weight of Mg, which is not battery-grade (equilibrium potential of + 680 mv (S~E)).
In order to obtain a MnO2 quality that is comparable to the one obtained in example 1, it is necessary, as was found by the applicant, to make following additional operations (after filtration, washing, repulping in water at 70~C, filtration and washing, as performed in example l) :
repulping the cake in diluted (20 g/l) sulphuric acid (200 g of cake per litre), filtration, washing wit~ lO 1 of a lO g/l Na2CO~ solution, and washing with lO0 1 of water.
Example 3 The same mode of operation as in example l is used, but MnO2 is precipitated under atmospheric pressure, i.e. by having the chlorine bubbled in the solution.
The MnO2 quality obtained is comparable to that obtained in example l. MnO2 precipitation lasted however 15 hours while in example l this precipitation only lasted 2 hours.
.
.~: , ~.: : " . . , : - .
- discharge conditions : 5 minutes/hour during 10 hours/day on a 5 ohm resistance till the potential at the battery terminals drops to 0.9 V
- discharge time : 7 hours It is to be noted that in the same conditions a commercial battery grade MnO2 has given a discharge time of 6.5 hours.
Example 2 _________ The same mode of operation as in example 1 is used, but the MnO2 precipitate i6 not digested under chlorine pressure.
'' ~ ~ -' ' '- ' '; ~
s The MnO2 precipitate is thus immediately filtered as soon as no more Mg(OH)2 is added.
The filtration cake is processed in the same way as in example l and it is stated that the thus obtained MnO2 contains-e~ percent in weight of Mg, which is not battery-grade (equilibrium potential of + 680 mv (S~E)).
In order to obtain a MnO2 quality that is comparable to the one obtained in example 1, it is necessary, as was found by the applicant, to make following additional operations (after filtration, washing, repulping in water at 70~C, filtration and washing, as performed in example l) :
repulping the cake in diluted (20 g/l) sulphuric acid (200 g of cake per litre), filtration, washing wit~ lO 1 of a lO g/l Na2CO~ solution, and washing with lO0 1 of water.
Example 3 The same mode of operation as in example l is used, but MnO2 is precipitated under atmospheric pressure, i.e. by having the chlorine bubbled in the solution.
The MnO2 quality obtained is comparable to that obtained in example l. MnO2 precipitation lasted however 15 hours while in example l this precipitation only lasted 2 hours.
.
.~: , ~.: : " . . , : - .
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of battery-grade manganese dioxide which comprises:
(a) contacting a manganese chloride solution with chlorine, while maintaining the pH of the solution between 0.5 and 3 by adding MgO and/or Mg(OH)2 so as to thereby produce a MgCl2 solution poor in manganese and which contains a MnO2 pre-cipitate that is contaminated by magnesium;
(b) allowing the MnO2 precipitate to digest in said MgCl2 solution in the presence of chlorine under pressure in an autoclave so as to reduce substantially the magnesium content of said MnO2 precipitate, (c) separating the digested MnO2 precipitate from the MgCl2 solution, (d) washing and drying the MnO2 precipitate.
(a) contacting a manganese chloride solution with chlorine, while maintaining the pH of the solution between 0.5 and 3 by adding MgO and/or Mg(OH)2 so as to thereby produce a MgCl2 solution poor in manganese and which contains a MnO2 pre-cipitate that is contaminated by magnesium;
(b) allowing the MnO2 precipitate to digest in said MgCl2 solution in the presence of chlorine under pressure in an autoclave so as to reduce substantially the magnesium content of said MnO2 precipitate, (c) separating the digested MnO2 precipitate from the MgCl2 solution, (d) washing and drying the MnO2 precipitate.
2. A process according to claim 1 wherein the chlorine pressure is at least 2 kg/cm2 in step (b).
3. A process according to claim 2 wherein the chlorine pressure is between 2.5 and 6 kg/cm2.
4. A process according to claim 1 wherein step (b) lasts at least 1 hour.
5. A process according to claim 4 wherein step (b) lasts from 2 to 4 hours.
6. A process according to claim 1 wherein chlorine under pressure is used in step (a).
7. A process according to claim 6 wherein the chlorine pressure is between 1.5 and 4.5 kg/cm2 in step (a).
8. A process according to claim 1 wherein chlorine under atmospheric pressure is used in step (a).
9. A process according to claim 1 wherein the solution resulting from step (a) contains 10 to 20 g/l of manganese.
10. A process according to claim 1 wherein the solution resulting from step (a) contains 85 to 100 g/l of magnesium.
11. A process according to claim 1 wherein in step (a) MgO and/or Mg(OH)2 is added as a suspension in a MgCl2 solution.
12. A process according to claim 11 wherein the MgCl2 solution, in which the MgO and/or Mg(OH)2 is put into suspension, contains 90 to 110 g/l of Mg.
13. A process according to claim 11 wherein the suspension contains 360 to 480 g of Mg as MgO or Mg(OH)2 per litre.
14. A process according to claim 11 wherein MgO and/or Mg(OH)2 is added to the solution resulting from step (c) so as to pre-cipitate the manganese as an hydroxide and to produce an almost manganese free MgCl2 solution, the precipitate is separated from the demanganized MgCl2 solution, and at least part of this de-manganized MgCl2 solution is subjected to a pyrohydrolysis whereby producing MgO and HCl.
15. A process according to claim 14 wherein part of said de-manganized MgCl2 solution and part of said MgO are used to prepare said suspension of MgO and/or Mg(OH)2 in a MgCl2 solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| LU80477 | 1978-11-06 | ||
| LU80477 | 1978-11-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109645A true CA1109645A (en) | 1981-09-29 |
Family
ID=19729037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA339,079A Expired CA1109645A (en) | 1978-11-06 | 1979-11-02 | Process for the production of battery-grade manganese dioxide |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4284618A (en) |
| CA (1) | CA1109645A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232490A (en) * | 1985-11-27 | 1993-08-03 | Leadville Silver And Gold | Oxidation/reduction process for recovery of precious metals from MnO2 ores, sulfidic ores and carbonaceous materials |
| US6517899B1 (en) | 1995-01-20 | 2003-02-11 | Engelhard Corporation | Catalyst and adsorption compositions having adhesion characteristics |
| US6200542B1 (en) | 1995-01-20 | 2001-03-13 | Engelhard Corporation | Method and apparatus for treating the atmosphere |
| US6818254B1 (en) * | 1995-01-20 | 2004-11-16 | Engelhard Corporation | Stable slurries of catalytically active materials |
| US6863984B2 (en) | 1995-01-20 | 2005-03-08 | Engelhard Corporation | Catalyst and adsorption compositions having improved adhesion characteristics |
| US20020018742A1 (en) * | 1995-01-20 | 2002-02-14 | Engelhard Corporation | Method and apparatus for treating the atmosphere |
| US20030166466A1 (en) * | 1995-01-20 | 2003-09-04 | Hoke Jeffrey B. | Catalyst and adsorption compositions having improved adhesion characteristics |
| AU4701196A (en) | 1995-01-20 | 1996-08-07 | Engelhard Corporation | Pollutant treating device located in vehicle compartment for cleaning ambient air |
| US6214303B1 (en) | 1995-01-20 | 2001-04-10 | Engelhard Corporation | Method and apparatus for treating the atmosphere |
| US5997831A (en) * | 1996-07-12 | 1999-12-07 | Engelhard Corporation | Method of catalytically treating the atmosphere and heat exchange devices produced thereby |
| US5836524A (en) * | 1996-10-01 | 1998-11-17 | National Science Council | Liquefaction of wastes with product oil recycling |
| US6156283A (en) * | 1998-03-23 | 2000-12-05 | Engelhard Corporation | Hydrophobic catalytic materials and method of forming the same |
| USH2121H1 (en) | 2000-10-13 | 2005-08-02 | The United States Of America As Represented By The Secretary Of The Navy | High surface area, nanoscale, mesoporous manganese oxides with controlled solid-pore architectures and method for production thereof |
| US7718319B2 (en) | 2006-09-25 | 2010-05-18 | Board Of Regents, The University Of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB597824A (en) * | 1944-03-06 | 1948-02-04 | Cie De Prod Chim Et Electro Me | Method of manufacture of depolarizing manganese dioxides |
| US2473563A (en) * | 1944-03-06 | 1949-06-21 | Alais & Froges & Camarque Cie | Preparation of manganese dioxide |
| US3414440A (en) * | 1964-09-02 | 1968-12-03 | Dow Chemical Co | Gamma manganese dioxide, method of preparing and dry cell type battery employing gamma type manganese dioxide |
| ZA718300B (en) * | 1970-12-30 | 1972-09-27 | Broken Hill Pty Co Ltd | Processing of manganese ores |
| US4150091A (en) * | 1977-11-21 | 1979-04-17 | Sun Ocean Ventures, Inc. | Manganese ore leaching process |
-
1979
- 1979-10-22 US US06/086,713 patent/US4284618A/en not_active Expired - Lifetime
- 1979-11-02 CA CA339,079A patent/CA1109645A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4284618A (en) | 1981-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1109645A (en) | Process for the production of battery-grade manganese dioxide | |
| CA1141172A (en) | Removal of manganese ions from zinc and manganese containing solutions | |
| US5091161A (en) | Production of pure magnesium chloride solution from siliceous magnesium minerals | |
| US4067789A (en) | Process for manganese removal from zinc metal bearing solutions | |
| KR20200059191A (en) | Methods for the production of cobalt and related oxides from various feed materials | |
| US2398493A (en) | Production of magnesium chloride from serpentine | |
| US3770868A (en) | Processing of manganese ores | |
| US3962051A (en) | Atmospheric leaching of matte containing iron | |
| US4489043A (en) | Manufacture of manganous sulfate solutions | |
| US3652265A (en) | Recovery of metal values from nickel-copper mattes | |
| US4070260A (en) | Process of sulfuric acid leaching silicated zinc ores | |
| CN116409768A (en) | Method for recycling positive electrode of iron phosphate battery | |
| CA2634876C (en) | Methods of making and washing scorodite | |
| US3667906A (en) | Method for producing manganese dioxide containing less potassium | |
| US2835558A (en) | Recovery of selenium | |
| US4272490A (en) | Hydrometallurgical process for the treatment of ores | |
| US3933976A (en) | Nickel-cobalt separation | |
| US4485073A (en) | Process of producing manganese sulfate solutions | |
| CA1102556A (en) | Production of titanium metal values | |
| CN117712533A (en) | Treatment method and application of waste lithium iron manganese phosphate battery | |
| EP0131810B1 (en) | Process for recovering cesium from pollucite | |
| CA1135213A (en) | Cathodic dissolution of cobaltic hydroxide | |
| US4151258A (en) | Dissolution of cobaltic hydroxide with organic reductant | |
| US3288597A (en) | Process for the recovery of certain metallic and non-metallic constituents of waste slag from reverberatory refining of copper pyritic type ores | |
| US4798623A (en) | Method for producing fine cobalt metal powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19980929 |