US3864118A - Method for producing manganese oxide pellets - Google Patents

Method for producing manganese oxide pellets Download PDF

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US3864118A
US3864118A US330367A US33036773A US3864118A US 3864118 A US3864118 A US 3864118A US 330367 A US330367 A US 330367A US 33036773 A US33036773 A US 33036773A US 3864118 A US3864118 A US 3864118A
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manganese
concentrate
magnetic
oxide
iron
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Charles R Schumacher
Ezekiel Dominguez
Gordon H Crouch
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Bethlehem Steel Corp
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Bethlehem Steel Corp
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Priority to IN2278/CAL/73A priority patent/IN140097B/en
Priority to AU61497/73A priority patent/AU487671B2/en
Priority to ZA738147*A priority patent/ZA738147B/xx
Priority to OA55112A priority patent/OA04594A/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing

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  • Simitz 57 1 ABSTRACT Method for producing manganese oxide pellets from manganesebearing material such as high grade, medium grade or low grade oxidic or carbonate manganese ores and from waste products which are obtained from high grade and medium grade manganese ore processing plants.
  • the manganese-bearing material is beneficiated to form an upgraded concentrate which includes manganese oxides and non-magnetic iron oxides.
  • the concentrate is roasted to reduce the manganese oxides to mangano-manganic oxide and to reduce a major portion of the non-magnetic iron oxides to magnetic iron oxides.
  • the roasted concentrate is ground and treated magnetically to separate nonmagnetic particles from magnetic particles.
  • the ground non-magnetic particles are flocculated, thickened and filtered to thus produce a non-magnetic concentrate which may be partially dried and which is balled and pelletized.
  • Manganese oxide pellets produced by the method of the invention consist of not less than 48% manganese, not more than 4.0% silica, not more than 7.0% alumina, not more than 1.0% alkali metals, not more than 0.12% arsenic and not more than 6.0% iron, the weight ratio of the manganese to iron in the pellets is between 8:1 to about 20:1.
  • the ore in these deposits is processed by simple mechanical ore preparation operations, such as primary and secondary crushing, screen ing and washing, to produce a product containing more than 48% manganese, a low incident of impurities and a favorable manganese to iron ratio.
  • the product is commercially attractive and can be used to produce manganese alloys, such as ferro-manganese and the like.
  • the ore deposits which contain less than 35% and which can contain as little as manganese are classified as low grade ores. If the iron content is high, the ores are referred to as manganiferous ores. Generally, these low grade ores and waste products for high grade and medium grade manganese ore processing plants are not used in producing manganese alloys, such as ferro-manganese and the like, because of the low manganese content, the high gangue content and an unfavorable or low manganese to iron ratio.
  • the bailed material is fired at about 2300F. for a time in a reducing or neutral atmosphere, containing little or no .oxygen, to reduce the manganese oxide on the surface of the ore particles to MnO and to react the MnO with the acidic impurities, for example, alumina and silica, to form a slag which binds the pellets together.
  • the above method can be used with high grade manganese ores and concentrates containing small amounts of gangue such as alumina, silica, alkali metals and arsenic, the method cannot be used with ores which contain large quantities of the above impurities since these impurities are not removed in the process.
  • the formation of a slag in the pellets coats and binds the pellets together at relatively low temperatures such as 2000 F. to 2300 F. making it virtually impossible to reduce the arsenic content of the pellets even at temperatures as low as 2300 F. in a reducingatmosphere within a commercially accepted residence time at temperature.
  • the presence oflarge amounts of slag-forming constituents in the pellets requires the addition of large amounts of flux materials, such as calcium carbonate, to the blast furnace during subsequent reduction of the manganese ores to ferro-manganese, thereby increasing the costs of production of the ferro-manganese alloys. Since the amount of alkali metals in the treated manganese material is not reduced, the hazards of early refractory lining failure due to refractory attack during reduction of the treated material in the blast furnace is an ever present danger.
  • Manganese ores such as manganiferous iron ores which contain about 8% to 16% manganese and 12% to 35% iron and other low grade deposits, are reduction roasted to produce leachable manganous oxide.
  • the manganese ores are roasted in a shafttype furnace to convert all the manganese dioxide to manganous oxide and iron oxides to magnetite. All the manganous oxide is leached from the roasted material by an ammoniacal leaching process.
  • the manganese ores contain arsenic, it is necessary to remove substantially all the arsenic prior to the use of the manganese ores in the production of manganese and ferro-manganese alloys. Arsenic remaining in the ore is released as a vapor during the smelting of the manganese ores in the blast furnace. This arsenic is deposited in the gas flues of the furnace and is eventually vented to the atmosphere. Therefore, as an environmental control measure, the arsenic in the manganese ores should be removed prior to use in the metallurgical furnaces.
  • the method of the invention includes mechanical and gravity beneficiating of oxides and carbonate manganese ores and waste products from manganese ore processing plants to obtain a concentrate which is high in manganese content and subjecting the concentrate to reduction roasting to produce magnetic and non-magnetic particles in the concentrate.
  • the roasted concentrate is treated magnetically to separate the magnetic particles from the non-magnetic particles and to form both a concentrate of non-magnetic particles and a concentrate of magnetic particles.
  • the magnetic concentrate is discarded.
  • the non-magnetic concentrate is then further processed to produce manganese oxide pellets which are commerically attractive and are suitable for use in producing manganese alloys such as ferro-manganese and the like.
  • the drawing is a schematic diagram of the method of the invention by which oxidic and carbonate manganese ores and waste products from oxidic and carbonate manganese ore processing plants are formed into usable manganese oxide pellets.
  • not more than 6% iron and having a manganese to iron weight ratio of not less than 8: I can be made from (a) high grade and medium grade oxidic manganese ores in which the primary manganese mineral is pyrolusite (Mn O) or the potassium bearing mineral, cryptomelane (KMn O such as Brazilian ICOMI ore, (b) high grade and medium grade carbonate manganese ores in which the primary manganese mineral is rhodochrosite (MnCO (c) low grade manganese ores which can contain pyrolusite or rhodochrosite or psilomelane (Ba H O)- Mn O, and (d) waste products from high grade and medium grade oxidic and carbonate manganese ore processing plants.
  • the oxidic and carbonate manganese ores and waste products which can be pelletized by the method of the invention, have a chemical composition within the broad ranges shown below in Table I:
  • Manganese is calculated as elemental manganese, iron is calculated as elemental iron, sodium and potassium are calculated as oxides (Na O and K 0, respectively), silica is calculated as SiO and alumina is calculated as A1 0 and arsenic as elemental arsenic.
  • the percentages of the constituents reported in these specifications and claims are on a weight basis unless otherwise noted.
  • Magnetic iron oxide Fe O is reduced to magnetic Constituent %in Product iron oxide (Fe O
  • the magnetic iron oxide Fe O Medium Fine Size I i I size Particles Punides can be separated from the non-magnetic particles such as manganese oxide particles and iron oxide (Fe O Manganese 3(t-4o 28-42 particles in the roasted concentrate by magnetic 3: ⁇ , 311; means, such as magnetic separators, to thereby reduce Alumina 7-10 10-13 the amount of iron and increase the amount of mangagg l 'z jajfig Z22 nese in the concentrate to thereby obtain a favorable Phosphorus About .1 About .1 manganese to iron weight ratio.
  • the non-magnetic concentrate can stored. be processed in subsequent steps to produce manga-
  • the medium and fine size partinese oxide pellets which can be used to produce mancles mentioned above can be beneficiated and proganese alloys.
  • a manganese oxide concentrate which can
  • the manganese concentrate that is, the mixture of be processed into manganese oxide pellets containing medium and fine particles which have been treated in a high manganese content, low iron and other impurithe gravity-type separators, is reduction roasted in a ties content and a desirable manganese to iron weight two-step process in a fluid solids reactor.
  • the mangaration of not less than 8:1.
  • the pellets can be used to nese concentrate is dried in an upper compartment of produce manganese alloys such as ferromanganese althe fluid solids reactor and is passed to a lower comloys and the like.
  • media dynawhirlpools can be used for medium size par- Turning now to the attached FIGURE, the concenticles and Humphreys Spirals for fine size particles.
  • the sodium strictlye 10 from the dynawhirlpools (not shown) and Humphrey's Spirals (not shown) is fed to a fluid solids reactor 14 by means of a conveyor system 11 and 12 and a chute 13 above the fluid solids reactor 14.
  • concentrate 10 drops from the conveyor 12 into the chute 13 which feeds the concentrate 10 into an upper or preheating compartment 15 of the fluid solids reactor 14.
  • the particles of the concentrate 10 are dried, dispersed and form a fluid bed 16 on the upper dome 17 by hot combustion gases flowing upwardly through the fluid bed from the hot wind box 18.
  • the hot combustion gases which are at a temperature of about 1022 F to about 1500 F. (500 C to 815 C) flow from the hot windbox l8 upwardly through a plurality of slots 19 in the upper dome l7 and heat the fluid bed 16.
  • a space or free board 20 is provided above the fluid bed 16 in the upper compartment 15.
  • the concentrate is heated to a temperature of about 302 F. to about 392 F. 150 C-200 C).
  • the two-step roasting process is continuous, that is, concentrate 10 is continuously fed onto the top of the fluid bed 16 in the upper compartment 15 of the fluid solids reactor l4'and a steam of preheated concentrate is continuously drawn out of the upper compartment 15 from the bottom of the fluid bed 16 and is fed to a second fluid bed 22 in the lower compartment 23 of the fluid solids reactor 14 by means of conduit 21.
  • the free moisture in the concentrate which can be about 5% to about l5% based on the weight of the concentrate, isndriven off and the preheated concentrate which is drawn off from the upper compartment at a temperature of about 392 F. (200 C) is bone dry. A portion of the water of hydration, about one tenth thereof, is also removed from the concentrate in the upper compartment 15.
  • the dried concentrate is transferred from the upper compartmentlS to the lower compartment 23 of the fluid solids reactor 14 and is discharged onto the lower dome 24 in the lower compartment 23 to form a relatively deep fluid bed 22.
  • a large free board 25 is provided in the lower compartment 23 above the fluid bed 22.
  • An air blower 26 supplies fluidizing air at a temperature of about 158 F. to 194 F. (70 C to 90 C) to a cold wind box 27 from which the air is blown upwardly through the fluid bed 22 by means of a plurality of slots 28 in the lower dome 24.
  • Fuel oil for example, No/ 6 oil, is incompletely burned at the bottom of the fluid bed 22 in the lower compartment 23.
  • the concentrate is preferably heated to a temperature range of about 1292 F. to 1391 F.
  • the first decomposition of the cryptomelane (KMn O is to manganic oxide (Mn O and the second decomposition is to the tetragonal crystalline form of hausmannite, which is manganomanganic oxide (Mn O A major portion of the non-magnetic iron oxide F6 0,) is reduced to magnetic iron oxide (Fe O A minor portion of the mangano-manganic oxide (Mn 0,) is reduced to manganous oxide (MnO). Because at elevated temperatures, for example, 1598 F. to 1800 F.
  • the concentrate is preferably roasted at a temperature within the range of about 1292 F. to 139l F. (700 C to 755C however, the roasting process in the lower compartment 23 is operative within a temperature range of about 1 1 12 F. to 1598 F. (600C to 870 C).
  • the fluidizing and combustion air is passed upwardly into the fluid bed 22 through slots 28 in the lower dome 24 of the cold wind box 27.
  • the amount of air passed upwardly through the slots 28 is sufficient so that the air space velocity is high enough to fluidize the coarser particles of concentrate.
  • the exit gases in the atmosphere in the free board 25 above the fluid bed 22 in the lower compartment 23 of the reac tor 14 should contain a high percentage of carbon dioxide and a low percentage of oxygen to obtain the most beneficial results of the invention.
  • the exit gases from the roasting step should contain about 28% to about 30% carbon dioxide, about 0.5% to about 1% oxygen, about 0.5% to about 1% hydrogen and carbon monoxide and about 0.5% to about 1% methane.
  • the amount of oxygen present in the exit gases in the free board 25 which are cycled into the upper drying'portion of the fluid solids reactor 14 is indicative of the manganese to iron ratio which can be expected in the concentrate after magnetic separation.
  • the amount of oxygen in the exit gases is controlled by the amount of fuel which is burned in the fluid bed 22 in the lower compartment 23 of the reactor 14.
  • manganese to iron ratio in the manganese concentrate after magnetic separation varies inversely with the amount of oxygen in the exit gases in the free board 25, that is, high oxygen contents indicate low manganese to iron ratios, for example, 3:1, and low oxygen content favors high manganese to iron ratios, for example 8:1 or more.
  • Oxygen contents in the exit gases of about 5% result in a manganese to iron ratio of about 5:1 whereas oxygen contents of 3.0% and 1.0% or less result in a manganese to iron ratio of about 12:1 and 15:1 or higher, respectively.
  • the iron oxide (Fe OQpresent in the concentrate as non-magnetic iron oxide is reduced to ferrous-ferric 'iron oxide [(Fe O which alternatively can be written (FeO.Fe O which is a magnetic iron oxide, in the lower compartment 23, according to the following reaction:
  • Pelletizing manganese dioxide causes oxygen to be released during the (1) 3 Fe O to the following reactions: thermic decomposition of the manganese dioxide heat 2 2 MnO T 2 950F.(510C) 2 3 1/2 2 (00) heat (00 (3) 3 2 3 (H 1 l O 0 F.I7bO C3 3 i (H 5) of course, a minor portion of the mangano-manganic (MnO to mangano-manganic oxide (Mn O.). The reoxide (Mn O is reduced to manganous oxide (MnO).
  • Reaction g ng Such as alumina and i a, I'm iquids at l W (3) above is accomplished at relatively low temperatemperatures, the removal of a substantial portion of tures such as 1400" F, (760C) b th use f d i the gangue prevents the fusion of the pellets during the atmosphere containing carbon monoxide (CO) d b final high temperature heating stage to remove arsenic.
  • tures such as 1400" F, (760C) b th use f d i the gangue prevents the fusion of the pellets during the atmosphere containing carbon monoxide (CO) d b final high temperature heating stage to remove arsenic.
  • the concentrate begin to fuse together and sinter at potassium and sodium, attack the refractory lining in a temperatures of about l472 F. (800 C).
  • the op d um and potassium decreases the danger of refractory eration of the fluid bed is physically upset because h attack when pellets of the invention are treated in the flow of gases upwardly through the bed is effectively blast furnace.
  • Sodium is usually associated with the alusto ped, hence reduction of either i id or mina and silica and hence is removed with gangue durganese oxide cannot take place.
  • sinter is ing washing and gravity concentration steps.
  • the low nary means such as washing since the mineral is insolu- 40 Order e iig a or of hausmannite to 2250 F. ble in water.
  • the potassium atom is trapped and ranin a neutral 0r ligh ly ed cing a mosphere domly distributed in the crystal lattice of the cryptomeor to 2650 F. (1454 C) in an oxidizing atmosphere, lane to maintain ionic balance and cannot be expelled a thermic allotropic change to a well defined ubi from the crystal lattice.
  • it ha be form occurs in the hausmannite.
  • arsenic is rejected from the hausmanis broken down in the two-step reduction roasting to nite crystal.
  • K 0 water soluble potassium oxide
  • Arsenic is a of mangano-manganic xid (M 0 a c din to th tramp element in both iron and steel and therefore its following reaction: removal or reduction to a minimum is essential.
  • the concentrate can contain both iron oxides and maninvolving slurring with water.
  • the concentrate is passed to magnetic pellets during elevated heating for arsenic removal. separators 30 where substantially all the magnetic iron.
  • the explosive release of water ofhydration has resulted oxide (Fe O.,) particles are separated from the nonin the failure of several previous attempts to produce magnetic iron oxide (Fe O and manganese oxide particles to form a magnetic concentrate and a nonmagnetic concentrate.
  • the magnetic iron oxide (Fe O concentrate is passed to storage for future use as a source of iron or can be discarded as waste material.
  • the magnetic concentrate Since the magnetic concentrate has a high iron oxide content it can be beneficiated and processed into iron oxide or metallic iron pellets and it is therefore preferred to store the concentrate; Of course, the mag netic iron oxide (Fe O concentrate will usually contain some residual manganese oxides. This, however, is an advantage in the future use of this waste material as a source of iron to produce steel.
  • the non-magnetic manganese concentrate is flocculated with lime to improve the settling characteristics of the particles in the non-magnetic concentrate. it has also been found that lime introduced to flocculate the non magnetic manganese concentrate combines with the manganese oxides during pelletizing to form a refractory calcium manganate.
  • a dense shell of manganous oxide forms on pellets made from a concentrate with low lime additions. It is, therefore, preferred to add about 1.5% lime to the non-magnetic manganese concentrate during the flocculating step.
  • the flocculated non-magnetic manganese concentrate is thickened in a thickner 31 and filtered in filter 32 to produce 'a filter cake.
  • the filter cake is partially dried in drier 33 and is passed to a balling apparatus 34, such as a balling cone, disc, drum, flying saucer or the like.
  • a balling apparatus 34 such as a balling cone, disc, drum, flying saucer or the like.
  • No binders are generally required to ball the nonmagnetic manganese concentrate, however, binders such as bentonite can be used to ball the non-magnetic manganese concentrate if desired.
  • the non-magnetic manganese concentrate contains more than about 16% moisture, it is dried prior to balling. Drying is not required if the non-magnetic manganese concentrate contains about 8% to 14% moisture.
  • the nonmagnetic manganese concentrate contains less than 8% moisture, sufficient moisture to obtain about 8% to 14% moisture, based on the surface area of the particles in the non-magnetic manganese concentrate, is addedto the non-magnetic manganese concentrate before balling.
  • the non-magnetic manganese concentrate is formed into balls varying in size from one-fourth inch in diameter to three-fourths inch in diameter.
  • the balled non-magnetic manganese concentrate is fed onto a roller screen feeder 35 to remove the minus one-fourth inch fraction of fines and.to feed the inch balls into a pelletizing furnace 36, such as a multizon'ed travelling grate furnace or the like.
  • the balls are initially dried in the pelletizing grate at an air temperature of about 500 F. to about 800 F. to remove free moisture from the balls. 1f the balls are charged into a multi-zoned travelling grate furnace the drying can occur in the first or first and second zones of the furnace.
  • the balls should be dried at a rate sufficiently slow to prevent disintegration of the balls by vaporized moisture driven off in the drying stage.
  • the time can vary from as little as three mintues to as much as ten minutes dependent upon the amount of moisture to be removed and the temperature of the hot gases which are passed through the bed of moist balls.
  • the balls are then preheated to a temperature of about 1650 F. to about 1800 F. for a time, for example, about 5 minutes. by hot combustion gases passing downwardly through the balls. In a multi-zoned travelling grate furnace this stage would occur in the third zone of the furnace.
  • the balls After preheating, the balls are heated by. hot combustion gases passing downwardly through the bed of balls to heat them to a temperature range of about 2200 F. to 2650 F. wherein the balls will be hardened to form pellets and a major portion of the arsenic removed from the pellets.
  • the pelletizing stage In this stage of pelletizing in a multizoned travelling grate furnace, the pelletizing stage is divided into a first portion occurring in the fourth zone of the furnace and a second portion occurring in the fifth zone of the furnace. In the first portion of the fourth zone the balls are heated to between about 2200 F. to about 2450 F. for a time, for example, 20 minutes, and are hardened to form pellets.
  • the pellets are heated to between about 2450 F. and 2650 F. (1342 C to 1454 C) for a time, for example, about 5 minutes. Additional hardening of the pellets occurs and a major portion of the arsenic in the pellets is volatilized and removed from the furnace in the waste hot combustion gases. Because the waste hot combustion gases contain arsenic, the gases are exhausted either to the atmosphere or to a suitable pollution control apparatus.
  • the pellets are then cooled by cooling air which is passed upwardly through the pellet bed for a time to reduce the temperature of the pellets to about F., at which temperature the pellets are discharged from the furnace.
  • cooling air In a multi-zoned travelling grate furnace the cooling stage will occur in a fifth zone of the furnace and will occur in two stages. In the first stage the pellets will be cooled to about 1800 F. which can take, for example, about 10 minutes.
  • the cooling air contains arsenic and is therefore passed to waste with the waste hot combustion gases from the arsenic removal stage.
  • the pellets are further cooled to about 150 F. in a second cooling stage. Gases from this stage can be recycled and reheated to be reused in the drying, preheating and pelletizing steps.
  • Pellets treated according to the method of the invention have a typical chemical composition as shown in Table V as follows:
  • manganese dioxide MnO
  • mangano-manganic oxide Mn O with a loss in weight ofabout 13%.
  • the mangano-manganic oxide (Mn O concentrate is soft, porous and poorly crystalline.
  • the balls formed from this material are porous and weak.
  • pelletizing balls of mangano-manganic oxide Mn O at temperatures of about 2200 F./2250 F. produced relatively weak pellets having a tumble index plus one-fourth inch) of 80% to 83% and a porosity of 20%.
  • the pellets are not strong enough to resistdegradation during transport.
  • balls of mangano-manganic oxide (Mn O separation are not strong enough to resistdegradation during transport.
  • balls of mangano-manganic oxide (Mn O separation are all the concentrates produced from the above ores must be roasted to accomplish the results of the method of the invention, that is, a major portion of the nonmagnetic iron oxide is converted to magnetic iron oxide which can be separated by magnetic means from the non-magnetic manganese oxides.
  • manganese ores which contain cryptomelane KMn,,O,,,
  • the insoluble potassium manganese oxide KMn O is decomposed into the water soluble potassium oxide (K 0) and mangano-manganic oxide (Mn O Water of hydration will be removed as well as oxygen.
  • Arsenic will be removed from pellets made from these ores when heated to temperatures of about 2550 F. to about 2650 F. without the formation of appreciable amounts of liquid slag.
  • roasting of the manganese ores prior to balling and pelletizing of the balls by high temperature treatment converts the manganese from a higher to a lower oxidation state so that an explosive release of oxygen from the oxidized manganese minerals such as MnO during high temperature treatment of the balled manganese material will not cause shattering or cracking of said balls.
  • Processing low grade manganese ores that is, ,those ores containing less than about 35% manganese, by the method of the invention requires grinding the ores to a liberation size and separation of the particles in gravity-type separators to upgrade the material prior to roasting.
  • 2400 F. produced pellets which begin to shrink, the particles coalesce and a less porous-more dense, wellbonded structure is formed. Heating the balls to higher temperatures up to 2650 F., the temperature at which arsenic is vaporized, causes the pellets to shrink still further, increases coalescence, decreases porosity to between 5% and 15% and increases the strength of the pellets. Balled mangano-manganic oxide (Mn O fired at 2550 F./2650 F. formed pellets having a tumble index of between 90% to 95%. The tumble index is an indication of the strength of the pellets.
  • pellets should' have a tumble index of more than 90% as determined by ASTM E-69 tumble test in which an amount of pellets, 2 pounds or 25 pounds, is charged into a drum which is 3 feet in diameter and 18 incheslong. The drum is rotated at 24 revolutions per minute for 200 revolutions. The material charged into the drum is screened on a A inch screen.
  • the percent of pellets which are one-fourth inch or larger in diameter is taken as the tumble index While we have described the invention in connection with the treatment and upgrading and pelletization of waste products from high grade manganese ore processing plants, it will be understood that the method of the invention is also applicable to pelletizing all upgraded oxidic and carbonate high grade and medium grade manganese ores having a manganese content of about to 50% manganese, about 10% to 15% iron, not more than 8% silica.
  • tons of medium size particles, inch X +20 mesh, (U.S. Series Sieve) and 30 tons of fine size particles, 20 mesh X 100 mesh, (U.S. Series Sieve) were processed in mineral jigs and Humphrey's Spirals respectively.
  • the chemical composition ofthe medium size particles and fine size particles before and after treatment is shown in the following table:
  • the medium size particles and fine size particles were mixed to form one composite batch.
  • the batch was dried and then fed continuously into a fluid-bed type roaster.
  • the particles were roasted at about 1500 F. in a reducing atmosphere containing CO and H The average retention time was about 20 minutes.
  • the particles were then ground in a ball mill to about 64% minus 325 mesh and about minus 65 mesh and passed to a magnetic separator for wet separation into magnetic particles and non-magnetic particles. About 14% of the particles based on the weight fed to the magnetic separators were separated as magnetic particles and were passed to storage.
  • the remaining 86% of the particles, classed as non-magnetic were flocculated with lime, the addition being about 2.0% lime based on the weight of the non-magnetic concentrate.
  • the flocculated nonmagnetic concentrate was filtered, partially dried and fed to a disc-type balling apparatus for balling.
  • the particles were formed into balls which average about fiveeighths inch in diameter in size and were charged into a pot-grate furnace in batches of about 60 pounds.
  • the balls were heated to a temperature of about 750 F. by hot gases passing upwardly through the balls.
  • the balls are dried in a second drying step wherein hot gases were passed downwardly through the balls to raise their temperature to about 650 F. for about 3 minutes.
  • the dried balls were then preheated in a third or preheating step.
  • the temperature of the balls was raised to about 1800 F. in about 2 minutes by hot gases passing downwardly through the balls.
  • the balls were heated in a fourth or heat hardening step.
  • the temperature of the balls was raised to about 2650 F. for about 17 minutes by hot gases passing downwardly through the balls, at which temperature a major portion but not all of the arsenic was removed from the pellets.
  • the balls have now been hardened into pellets.
  • the pellets were cooled in a fifth step to about 1800 F. by cooling gases passing downwardly through the pellets.
  • the pellets were cooled by cooling air passing upwardly through the pellets in a sixth step.
  • the temperature of the pellets was lowered to between 150 F. and 200 F.
  • the pellets were discharged from the furnace.
  • a chemical analysis of a sample of the pellets showed the pellets to have the following chemical compositon:
  • roasting the manganese oxide concentrate at a temperature for a time in a reducing atmosphere to reduce substantially all the manganese dioxide par- 7 ticles to mangano-manganic oxide and a minor portion of manganous oxide, to reduce a major portion of the non-magnetic iron oxide particles to magnetic iron oxide particles, and to remove substantially all the water of hydration,
  • step (a) is between about 1100 F. and about 1600 F.
  • step (f) O 0.5-1 H 0.5-l% CH 4.
  • the pelletizing temperature of step (f) is between about 2550 F. to about 2650 F.
  • step (g) 5. The method of claim 1 wherein the pellets in step (g) are cooled to a temperature between about 150 F. and about 200 F.
  • roasting the manganese concentrate at a temperature for a time in a reducing atmosphere to reduce substantially all the manganese compounds to mangano-manganic oxide and a minor portion of manganous oxide, and to reduce a major portion of the non-magnetic iron oxide particles to magnetic iron oxide particles and to remove'substantially all the water of hydration,
  • step (a) is about 1100 F. to about 1600 F.
  • step (a) 8. The method of claim 7 in which the exit gases from the roasting of step (a) contain: 28-30% CO 0.5l% O O.5l% CO, 0.5l.% H O, 0.5l% CH 9. The method of claim 6 in which the pelletizing temperature of step (g) is about 2550 F. to about 2650 F.
  • roasting the manganese oxide concentrate at a temperature for a time in a reducing atmosphere to decompose a substantial portion of the cryptomelane to manganese dioxide and potassium oxide, reduce substantially all the manganese dioxide particles to mangano-manganic oxide and a minor portion to manganous oxide, reduce a major portion of the non-magnetic iron oxide particles to magnetic iron oxide particles and to remove substantially all the water of hydration,
  • step (a) is about 1112 F. to 1598 F.
  • step (a) contains about 28-30% CO 0.5-l% O O.5-l% CO, 0.51% H 0.5-l% CH 13.
  • step (f) is about 2550 F. to about 2650 F.
  • step (b) roasting the manganese bearing concentrate of step (a) at a temperature for a time in a reducing atmosphere to decompose the cryptomelane to manganese dioxide and potassium oxide and to reduce substantially all the manganese dioxide particles to mangano-manganic oxide and a minor portion of manganous oxide and to reduce a major portion of the non-magnetic iron oxide particles to magnetic iron oxide particles and to remove substantially all the water of hydration,
  • non-magnetic manganese concentrate e. treating the non-magnetic manganese concentrate to remove a substantial portion of the potassium oxide and to produce a non-magnetic manganese concentrate suitable for balling
  • step (b) The method of claim 14 in which the roasting temperature of step (b) is about ll F. to about 1600 F.
  • step (b) contains 28-30% CO 0.51% O 0.5-1% CO, 0.5-1% H 0.5-1% CH 17.
  • step (h) is about 2550 F. to about 2650 F 18.
  • manganese oxide pellets consisting of not less than 48% manganese, not more than 4.0% silica, not more than than 7.0% alumina, not more than 1.0% alkali metals, not more than 0.12% arsenic and not more than 6.0% iron, said iron being present in a weight ratio of not less than 8 parts of manganese to one part ofiron and not more than 20 parts of manganese to one part iron and characterized by a porosity of about to 15% and a tumble index of 90% to 95%, from high grade, and medium grade oxidic and carbonate manganese ores, low grade oxidic and carbonate manganese ores and waste products from high grade and medium grade oxidic and carbonate manganese ore processing plants wherein said ores and waste products are beneficiated to form an upgraded manganese oxide concentrate containing about 35% to 50% manganese, about 10% to iron, about .1 8% to about .25% arsenic, not more than about 2.00% potassium and about 3% to about 8%
  • manganese oxide pellets containing not less than 48% manganese, not more than 6.0% iron, not more than 4.0% silica. not more than 7.0% alumina, not more than 1.0% alkali metals, not more than 0. 12% arsenic.
  • ferromanganese alloys from the group consisting of high grade manganese ores, medium grade manganese ores and low grade manganese ores, said ores containing arsenic and potassium, in the form of insoluble potassium compounds, wherein the manganese ores are upgraded in a physical ore processing plant to produce a manganese oxide concentrate containing about 35% to 50% manganese, about 10% to 15% iron, about .18% to about .25% arsenic and about 2.00% potassium, said pellets characterized by having a porosity of 5% to 15% and a tumble index of to said method comprising:
  • roasting the manganese oxide concentrate at a temperature for a time in a reducing atmosphere to reduce substantially all the manganese dioxide (MnO to manganese oxide (Mn O and a minor portion of manganous oxide (MnO) and a major portion of the non-magnetic iron oxide (Fe O to magnetic iron oxide (Fe O simultaneously converting a major portion of insoluble potassium compounds therein to water soluble potassium compound, and removing substantially all the water of hydration therefrom,
  • step (b) is 1 112 F. to 1598 F.
  • step (b) The method of claim 19 in which the roasting temperature of step (b) is 1292 F. to 1391 F.

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US330367A 1973-02-07 1973-02-07 Method for producing manganese oxide pellets Expired - Lifetime US3864118A (en)

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IN2278/CAL/73A IN140097B (fr) 1973-02-07 1973-10-15
AU61497/73A AU487671B2 (en) 1973-02-07 1973-10-17 Method for producing manganese oxide pellets
ZA738147*A ZA738147B (en) 1973-02-07 1973-10-19 Method for producing manganese oxide pellets
OA55112A OA04594A (fr) 1973-02-07 1974-02-01 Méthode pour produire des pellets d'oxyde de manganèse.

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Cited By (27)

* Cited by examiner, † Cited by third party
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US3942974A (en) * 1975-02-10 1976-03-09 Kennecott Copper Corporation Manganese nodule pelletizing
US4089928A (en) * 1976-03-30 1978-05-16 Eleusis Bauxite Mines-Mining Industrial And Shipping Inc. Method for increasing the MnO2 content of natural manganese dioxide ore
US4251265A (en) * 1979-07-27 1981-02-17 Reynolds Metals Company Clay preparation
US4274866A (en) * 1978-07-24 1981-06-23 Kennecott Copper Corporation Flotation and sintering of synthetic manganese carbonate
US4483828A (en) * 1984-02-08 1984-11-20 Kerr-Mcgee Chemical Corporation Method of producing manganese sulfate solutions of improved purity
US4485073A (en) * 1984-02-08 1984-11-27 Kerr-Mcgee Chemical Corporation Process of producing manganese sulfate solutions
US4489043A (en) * 1984-02-08 1984-12-18 Kerr-Mcgee Chemical Corporation Manufacture of manganous sulfate solutions
US5496526A (en) * 1993-08-30 1996-03-05 The United States Of America As Represented By The Secretary Of The Interior Production of intermediate grade manganese concentrate from low grade manganiferous ores
US5997831A (en) * 1996-07-12 1999-12-07 Engelhard Corporation Method of catalytically treating the atmosphere and heat exchange devices produced thereby
US6156283A (en) * 1998-03-23 2000-12-05 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US6200542B1 (en) 1995-01-20 2001-03-13 Engelhard Corporation Method and apparatus for treating the atmosphere
US6214303B1 (en) 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
US6340066B1 (en) 1995-01-20 2002-01-22 Engelhard Corporation Pollutant treating devices and methods of making the same
US20020018742A1 (en) * 1995-01-20 2002-02-14 Engelhard Corporation Method and apparatus for treating the atmosphere
US6517899B1 (en) 1995-01-20 2003-02-11 Engelhard Corporation Catalyst and adsorption compositions having adhesion characteristics
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
WO2010009527A1 (fr) * 2008-07-25 2010-01-28 Vale S.A. Procédé de production de granulés de manganèse à partir d'un minerai de manganèse non calciné et aggloméré obtenu suivant ce procédé
FR2946332A1 (fr) * 2009-06-05 2010-12-10 Kimpe Sarl Procede de fabrication d'oxyde de manganese
CN102305805A (zh) * 2011-07-29 2012-01-04 中南大学 一种球团生产过程中链篦机料层水分分布的检测方法
CN103205584A (zh) * 2013-04-15 2013-07-17 广西有色金属集团汇元锰业有限公司 一氧化锰矿粉的生产装置及其生产方法
CN103233243A (zh) * 2013-04-15 2013-08-07 广西有色金属集团汇元锰业有限公司 电解金属锰的生产方法
CN103725871A (zh) * 2014-01-26 2014-04-16 中南大学 一种强化高铁锰矿石铁锰分离的添加剂和方法
CN104023851A (zh) * 2011-08-01 2014-09-03 高级矿业资源有限公司 矿石加工
WO2015092137A1 (fr) * 2013-12-17 2015-06-25 Outotec (Finland) Oy Procédé et équipement destinés à préparer un concentré de minerai pour le bouletage
WO2015092136A1 (fr) * 2013-12-17 2015-06-25 Outotec (Finland) Oy Procédé permettant de produire des boulettes de minerai de manganèse
WO2016081173A1 (fr) * 2014-11-20 2016-05-26 Tronox Llc Procédé et appareil pour le grillage de minerai de manganèse

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US2074013A (en) * 1936-06-01 1937-03-16 Agnes Cornelison Bradley Process of treating ores and similar materials
US2296841A (en) * 1941-03-01 1942-09-29 Gardner Daniel Process for beneficiation of manganese ores
US2361925A (en) * 1942-07-04 1944-11-07 Minerals And Metals Corp Preparation of manganese products
US2745730A (en) * 1952-01-29 1956-05-15 Pickands Mather & Co Process of reducing manganese ores
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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3942974A (en) * 1975-02-10 1976-03-09 Kennecott Copper Corporation Manganese nodule pelletizing
US4089928A (en) * 1976-03-30 1978-05-16 Eleusis Bauxite Mines-Mining Industrial And Shipping Inc. Method for increasing the MnO2 content of natural manganese dioxide ore
US4274866A (en) * 1978-07-24 1981-06-23 Kennecott Copper Corporation Flotation and sintering of synthetic manganese carbonate
US4251265A (en) * 1979-07-27 1981-02-17 Reynolds Metals Company Clay preparation
US4483828A (en) * 1984-02-08 1984-11-20 Kerr-Mcgee Chemical Corporation Method of producing manganese sulfate solutions of improved purity
US4485073A (en) * 1984-02-08 1984-11-27 Kerr-Mcgee Chemical Corporation Process of producing manganese sulfate solutions
US4489043A (en) * 1984-02-08 1984-12-18 Kerr-Mcgee Chemical Corporation Manufacture of manganous sulfate solutions
US5496526A (en) * 1993-08-30 1996-03-05 The United States Of America As Represented By The Secretary Of The Interior Production of intermediate grade manganese concentrate from low grade manganiferous ores
US6340066B1 (en) 1995-01-20 2002-01-22 Engelhard Corporation Pollutant treating devices and methods of making the same
US6200542B1 (en) 1995-01-20 2001-03-13 Engelhard Corporation Method and apparatus for treating the atmosphere
US6214303B1 (en) 1995-01-20 2001-04-10 Engelhard Corporation Method and apparatus for treating the atmosphere
US20050100492A1 (en) * 1995-01-20 2005-05-12 Engelhard Corporation Vehicle having atmosphere pollutant treating surface
US20020018742A1 (en) * 1995-01-20 2002-02-14 Engelhard Corporation Method and apparatus for treating the atmosphere
US6517899B1 (en) 1995-01-20 2003-02-11 Engelhard Corporation Catalyst and adsorption compositions having adhesion characteristics
US7083829B2 (en) 1995-01-20 2006-08-01 Engelhard Corporation Vehicle having atmosphere pollutant treating surface
US6616903B2 (en) 1995-01-20 2003-09-09 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
US5997831A (en) * 1996-07-12 1999-12-07 Engelhard Corporation Method of catalytically treating the atmosphere and heat exchange devices produced thereby
US6156283A (en) * 1998-03-23 2000-12-05 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
US6586359B1 (en) 1998-03-23 2003-07-01 Engelhard Corporation Catalytic material for treating pollutant-containing gases
US6872686B2 (en) 1998-03-23 2005-03-29 Engelhard Corporation Hydrophobic catalytic materials and method of forming the same
WO2010009527A1 (fr) * 2008-07-25 2010-01-28 Vale S.A. Procédé de production de granulés de manganèse à partir d'un minerai de manganèse non calciné et aggloméré obtenu suivant ce procédé
US20120103134A1 (en) * 2008-07-25 2012-05-03 Vale S.A. Process to produce manganese pellets from non-calcinated manganese ore and agglomerate obtained by this process
US9181601B2 (en) * 2008-07-25 2015-11-10 Vale S.A. Process to produce manganese pellets from non-calcinated manganese ore and agglomerate obtained by this process
RU2519690C2 (ru) * 2008-07-25 2014-06-20 Вале С.А. Способ получения марганцевых окатышей из некальцинированной марганцевой руды и агломерат, полученный данным способом
FR2946332A1 (fr) * 2009-06-05 2010-12-10 Kimpe Sarl Procede de fabrication d'oxyde de manganese
CN102305805A (zh) * 2011-07-29 2012-01-04 中南大学 一种球团生产过程中链篦机料层水分分布的检测方法
CN102305805B (zh) * 2011-07-29 2012-12-19 中南大学 一种球团生产过程中链篦机料层水分分布的检测方法
CN104023851A (zh) * 2011-08-01 2014-09-03 高级矿业资源有限公司 矿石加工
CN104023851B (zh) * 2011-08-01 2016-08-31 高级矿业资源有限公司 矿石加工
CN103233243A (zh) * 2013-04-15 2013-08-07 广西有色金属集团汇元锰业有限公司 电解金属锰的生产方法
CN103205584A (zh) * 2013-04-15 2013-07-17 广西有色金属集团汇元锰业有限公司 一氧化锰矿粉的生产装置及其生产方法
WO2015092137A1 (fr) * 2013-12-17 2015-06-25 Outotec (Finland) Oy Procédé et équipement destinés à préparer un concentré de minerai pour le bouletage
WO2015092136A1 (fr) * 2013-12-17 2015-06-25 Outotec (Finland) Oy Procédé permettant de produire des boulettes de minerai de manganèse
CN105829551A (zh) * 2013-12-17 2016-08-03 奥图泰(芬兰)公司 用于制备锰矿石球团的方法
CN103725871B (zh) * 2014-01-26 2015-06-10 中南大学 一种强化高铁锰矿石铁锰分离的添加剂和方法
CN103725871A (zh) * 2014-01-26 2014-04-16 中南大学 一种强化高铁锰矿石铁锰分离的添加剂和方法
WO2016081173A1 (fr) * 2014-11-20 2016-05-26 Tronox Llc Procédé et appareil pour le grillage de minerai de manganèse

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AU6149773A (en) 1975-04-17
IN140097B (fr) 1976-09-11
OA04594A (fr) 1980-06-30

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