The method of processing of manganese ores

 

(57) Abstract:

The invention relates to ferrous metallurgy and can be used in the hydrometallurgical processing of manganese ore to concentrate manganese various purposes. The method includes the combined roasting-baking carbon-based material at 600-900oPre-crushed to a particle size of 0-5 mm mn containing ore with a ratio of vostanovitel : ore = 1: (1-6), processing SPECA 3,0-12 N abgaznaya hydrochloric acid containing 0.003 to 1.5 wt.% organically bound chlorine in 70-95oS and T:W= 1:(1,5-8: 0). Maintaining the pH of the mixture is less than 1.0, the solution decanted and adjusted the pH to 4.0 to 6.0, filtered hydroxides impurities. From a solution of manganese chloride (II) at 40-90oTo produce a concentrate of manganese at pH of 7.6-14,0 in the presence of an oxidant at a ratio of oxidant : ore = 1:(2,0-5,0), the concentrate is separated from the mother liquor, washed with hot water at T:W= 1: (2,5-3:5), filtered and dried. The method allows to process manganese ore of different mineralogical composition to high-quality concentrate manganese content not less than 60 wt.% manganese when removing it from the ore of at least 95% with a simultaneous increase step is Yanou acid. 3 C.p. f-crystals, 1 Il., table 4.

The invention relates to ferrous metallurgy and can be used in the hydrometallurgical processing of oxide, carbonate, blended manganese ore with obtaining a concentrate of manganese for various purposes.

Currently, the industry is processed, usually rich in manganese raw material, in which manganese more than 40 - 50%. For such materials, methods have been developed enrichment and extraction of manganese concentrate. It is of interest to poor processing or blended manganese ore with manganese content less than 35% to 8% iron, 25 - 40% silica, up to 1% sulfur and small amounts of Nickel, aluminum, calcium, copper, cobalt and other impurities. Such ores may consist of minerals of different types: pyrolusite, carbonates, manganite, rhodonite, psilomelan, chalcedony, quartz, etc.

There are different ways of processing such ores.

Known chemical methods of extraction of manganese from low-grade ores, and the composition of the reagents used in this case, due to the form of the mineral that forms the basis of a particular ore.

The prior art method of chemical enrichment oxide Carbo is a solution of calcium chloride in a ratio of 1: (3,0 - 3,5), pumping the resulting slurry for 0.5 - 1 h after the battery autoclave, heated to 200 - 220oC; then to the pulp add calcium chloride in the amount of 40 to 65% by weight solids and chloride iron to the concentration in solution of 2.0 - 2.5% and pumping the mixture through a second battery autoclave, heated to 200 - 250oC, the pulp is re-added iron chloride to the above concentration and pumping the mixture through the battery autoclave, heated to 240 - 260oC; the slurry is cooled to 90 - 100oC, is separated from the solid residue, the precipitated manganese from solution by pushenkoj, filtered, washed, calcined and doused or bitteroot.

The final product after calcination contains up to 60 - 64% manganese with significant impurity content:

the calcium oxide - 3 - 4%, calcium chloride is 3 - 5% to 1% of silicon oxide. Extraction of manganese in the final product 92 95.5 per cent.

The method has the following disadvantages:

1. Complicated in hardware design (uses 2 batteries autoclaves) and time-consuming.

2. The process requires a high temperature leaching.

3. The end product is a concentrate of manganese, purity and impurity content suitable only for the number of iron.

4. The method uses calcium chloride and iron chloride, which increases the process.

5. The degree of enrichment is not higher than 2.

(RF patent N 2090641 (IPC 6 22 47/00). The method of chemical enrichment oxide-carbonate ores. Priority from 11.02.93).

The closest to the invention in essence is a way of obtaining manganese concentrates, including leaching of manganese from the mn containing raw material inorganic acids (sulfuric or nitric) of the pre-enriched raw materials to concentrate manganese carbonate or oxide form with the contents of the oxides of manganese to 35%, neutralizing the resulting solution with the milk of lime to pH 4.5, the separation of the solid phase from the mn containing solution, introducing the solution of polyacrylic or polymethacrylic acid deposition concentrate manganese alkaline reagent, separating it from the mother liquor, washing repulpable at a ratio of t:W = 1:10, filtering and drying.

The final product contains from 45 to 60% of manganese when removing it to 75%.

The method has the following disadvantages:

1. The method requires a preliminary ore to the carbonate or oxide concentrates.

2. Uses polymer is of manganese in the final product depends on the content of manganese in the original concentrate.

4. The degree of enrichment not exceeding 1,5 - 1,8.

(USSR author's certificate N 1664 862 (IPC 5 C 22 47/00) the Method of obtaining manganese concentrates. Priority from 29.08.89).

Known in the art methods allow to extract manganese from different raw materials. However, they do not allow us to process the mn containing raw materials with different mineral composition and poor manganese ore without their enrichment.

The invention solves the problem of complex processing of raw materials of different mineralogical composition for one cycle with high-grade concentrate of manganese, including carbonate, oxide, oxide-carbonate and other mixed ore, including the poor in manganese content.

The technical result to be obtained by the use of the invention is the extraction of manganese from ores not less than 95%, with receipt for one cycle of high-grade concentrate of manganese, suitable for a wide range of use for content of not less than 60,0 wt.% manganese, the amount of impurities is less than 5% reduction in the production of concentrate from the use of cheaper reagent, in particular, abgaznaya hydrochloric acid, with the ri simultaneous provision of ecological safety of production with the processing of industrial waste.

This is achieved by a method for processing manganese ore, including the crushing ore, the translation into a solution of manganese and related impurities, the separation of the sludge, cleaning solution from impurities, the allocation concentrate manganese, followed by the separation from the mother liquor, filtering and drying. According to the invention the crushed ore is subjected to the combined roasting - baking carbon-based material at 600 - 900oC and the ratio of reducing agent : ore = 1:(1-6), spec process of 3.0-12 N abgaznaya hydrochloric acid containing 0.003 to 1.5 wt.% organically bound chlorine in 70-95oC and T:W= 1: (1,5-8: 0); in separated from the slurry solution was adjusted pH to 4.0 to 6.0, and produce a concentrate of manganese at 40-90oC simultaneously with the introduction of the oxidizer solution to establish a pH of 7.6-14,0 separated from the mother liquor concentrate manganese washed with hot water at T: W= 1:(2,5-3:5), the original ore is crushed to particle sizes 0-5 mm, the oxidation of Mn (II) conduct an oxidizer selected from the group of sodium hypochlorite, hydrogen peroxide, air, or mixtures thereof, at a ratio of oxidant : ore = 1:(2-5).

The method consists in the fact that pre-crushed to a particle size of 0-5 mm mn containing ore is sintered at 600-9070-95oC handle 3,0-12 N abgaznaya hydrochloric acid containing 0.003 to 1.5 wt.% organically bound chlorine, at T:W=1: (1,5-8,0) for 0.5-2 hours, maintaining the pH of the mixture is less than 1.

Then the solution is decanted, bring in the resulting solution pH to 4.0 to 6.0, the precipitate of hydroxides of impurities (iron, aluminium, copper, Nickel) is filtered off and washed with hot water. In the resulting solution is injected oxidant (from the group of sodium hypochlorite, hydrogen peroxide, air, or a mixture thereof) at a ratio of oxidant : ore = 1: (2.0 to 5.0) at a temperature of 40-90oC pH adjusted to 7.6 - 14,0, sludge concentrate manganese is separated from the mother liquor, washed with hot water at T:W = 1:(2,5-3,5), filtered and dried. The washing water return into circulation. The solid residue after leaching of manganese, traces of hydrochloric acid, used in construction, and the precipitate of hydroxides of impurities is also subject to further processing.

From the prototype to the invention is characterized by the fact that before the leaching of manganese milled to a particle size of 0-5 mm ore is subjected to the combined roasting-baking at 600-900oC carbon-based material with a ratio of reducing agent : ore = 1: (1-6), the sintered material is treated with 3,0-12,0 N abgaznaya hydrochloric acid is bound chlorine, after decanting the solution was adjusted pH to 4.0 to 6.0, after separation of the precipitate in the solution is injected oxidant and produce a concentrate of manganese at 40-90oC in the presence of an oxidant at a ratio of oxidant : ore = 1: (2-5) to establish a pH of 7.6-14,0, separate the concentrate of manganese from the mother liquor, washed with hot water at T:W = 1:(2,5-3,5), filtered and dried. The selection of the concentrate of manganese are in the presence of an oxidant selected from the group of sodium hypochlorite, hydrogen peroxide, air or mixtures thereof. The washing water return into circulation.

The inventive method allows you to extract up to 95% of manganese from ores containing 10-30% of manganese in different mineralogical forms, when the content of manganese oxides in concentrate not less than 94,8% by weight. The degree of enrichment is 2-6.

The method allows to process materials with complex structure, in particular, mixed manganese ore, without pre-enrichment and to obtain manganese concentrate gamma modification with the impurity content of less than 5%.

The modes of the method chosen experimentally.

Table 1 shows the results of the selection conditions of the firing-sintering of manganese ore.

Isledon ore sintering-sintering is 98% in the temperature range 600-900oC at a ratio of reducing agent : ore = 1: (1-6).

Table 2 shows the results of the selection conditions of acid treatment of the sintered raw material.

From table 2 it follows that the maximum recovery of manganese in the solution can be obtained only in certain intervals. Deviation from these intervals: concentration abgaznaya hydrochloric acid, T:W, treatment time and temperature reduces the extraction of manganese.

The drawing shows a plot of the precipitation of hydroxides of iron, manganese, aluminum, and zinc from the acidity.

Presents curves precipitation of hydroxides of iron, manganese, aluminum, and zinc obtained by the inventors experimentally show that at a pH of 4.0 to 6.0, a complete precipitation of iron, aluminium, zinc in the form of their hydroxides.

Table 3 shows the results of the selection conditions for the oxidation of manganese (+2) to manganese (+4).

From table 3 it can be seen that the deviations from intervals: the ratio of oxidant : ore, solution temperature and pH, can not achieve complete oxidation of the manganese.

Selection mode leaching of the concentrate are presented in table. 4.

Thus, the interval T:kerami.

Example 1. The source material is oxidized or carbonate manganese ore, composition, wt.%: manganese - 25, iron - 3.2, aluminum - 2,5, calcium - 1,5, sulfur - 1,0, silicon dioxide -28,0, phosphorus - 0.1, carbon - 1,0, copper - 0.8, Nickel is 0.1.

The ore is crushed to a particle size of 0 - 5 mm, mixed with coke in the ratio of ore : Cox = 5:1 and is sintered in a kiln at 750oC for 1 h, Cooled down to 100oC sintered material is ground in a mill wet grinding to a particle size less than 1 mm and treated in a sealed reactor 6,14 N abgaznaya hydrochloric acid containing 0.8 wt.% organically bound chlorine, 80oC and T:W = 1:2 over 1 h, maintaining a pH of less than 1 with constant stirring of the reaction mixture.

Extraction of manganese in the solution was 95%.

The resulting slurry defend 0,7 h, the solution decanted. Traces of hydrochloric acid, the solid residue is directed to the use in construction.

From a solution with a temperature of 70oC precipitated hydroxides of iron, Nickel, cobalt, aluminum, and copper to establish a pH of 4.0. Filtered on a suction filter the precipitate hydroxides of impurity metals is washed with hot (75-80oC) water. The precipitate is subject to accumulation for future: ore = 1:2.5 and continuous stirring, at a temperature of 40oC bring the pH to 9.0. Dedicated concentrate manganese filtered from the mother liquor and washed on a vacuum filter hot (60 - 80oC) water at t: W = 1:3, wring out the water filter type FPAKM and dried concentrate in a tumble dryer.

In the working area there are no pairs of hydrochloric acid.

The resulting concentrate contains manganese, wt.%: manganese is at least 60, iron - 0,3, silicon - 0.3, and carbon - 0,05, p is less than 0.001, sulfur - 0,1, lead - less 0,0005, chlorine - 0,08, moisture - 2,2.

The content of heavy metals (lead) is less than 0,0005%.

Received high manganese concentrate gamma modification.

Removing manganese from the ore is 95%. The degree of enrichment of 2.4. Through the extraction of manganese concentrate is 90%.

Example 2. The source material is mixed manganese ore composition, wt.%: manganese - 10,0, iron - 6,9, aluminum - 8,0, calcium - 0,35, sulfur to 0.18, silicon dioxide - 30,0, phosphorus - 0.03, carbon - 0.1, cu 0.1, Nickel of 0.01. Crushed to a particle size of 0 - 5 mm ore is mixed with coke in respect of ore : Cox = 3:1 and is sintered in a kiln at 900oC 1 o'clock Cooled sintered material is ground to a particle size less than 1 mm and handle h while maintaining the pH less than 1.0 and constant stirring of the reaction mixture. The pulp defend 0.3 hours, the solution decanted.

Extraction of manganese in solution is 94,8%.

The solid residue is rinsed from hydrochloric acid and filtered. Of the solution at 55oC precipitated hydroxides of impurity metals alkali to establish a pH of 6.0. Filtered and washed with hot water the precipitated hydroxides are sent for recycling.

In a solution of chloride of manganese (II) introducing the hydrogen peroxide at a ratio of hydrogen peroxide : ore = 1:5 and at a temperature of 60oC pH adjusted to 7.6. Dedicated concentrate manganese filtered from the mother liquor, washed with hot water at T:W = 1:2,5, wring out the water on the filter and dried concentrate. In the working area is not detected hydrochloric acid.

The resulting concentrate contains manganese, wt.%: manganese is at least 60, iron - 0.3, the silicon - 0.3, the carbon - 0.03, phosphorus, less than about 0.001, sulfur is less than 0.1, the lead - less 0,0005, chlorine - 0,06, moisture - 2,5. Extraction of manganese in concentrate from ore is 94,8%, the degree of enrichment 6. Through the extraction of manganese concentrate - 89,8%.

Example 3. The source material is mixed manganese ore composition, wt.%: manganese - 30, iron - 6,0, aluminum - 5.0, calcium - 2,0, sulfur and 0.8, silicon dioxide - 35,0, phosphorus - Oseni ore : Cox = 6:1 and is sintered in a kiln at 600oC 1 o'clock Cooled sintered material is ground to a particle size less than 1 mm and treated with 12 N abgaznaya hydrochloric acid at 95oC containing 0,003% of organically bound chlorine at 100oC and t:W = 1:1.5 V for 0.5 hours while maintaining a pH less than 1.0 and constant stirring of the reaction mixture. The pulp defend 1 h, the solution decanted.

Extraction of manganese in solution is 95%.

The solid residue is rinsed from hydrochloric acid and filtered. Precipitated hydroxides impurities to establish a pH of 5.6. Filtered and washed with hot water the precipitated hydroxides are sent for recycling.

In a solution of chloride of manganese (II) introducing a sodium hypochlorite with respect to the oxidant : ore = 1:2 and heated to 90oC the air, bring to 14.0 pH. Dedicated concentrate manganese filtered from the mother liquor, washed with hot water (60 -80oC) if t:W = 1: 3,5, wring out the water on the filter and dried concentrate.

The resulting concentrate contains manganese, by weight. % of manganese - not less than 60,0, iron - 0,5, silicon - 0,4, carbon - 0,04, p less than 0,001, sulfur - 0,09, chlorine - 0,08, moisture - 2,5. Removing manganese from the ore is 95,0%. The degree of enrichment 2.

Through the extraction of manganese in the party JSC "Soda".

Example 4. The source material is oxidized manganese ore, composition, wt. %: manganese - 14,7, iron - 8,1, aluminum is 2.7, calcium - 3,0, sulfur - 1,0, silicon dioxide - 39,8, phosphorus - 0.1, carbon - 1,0, copper and 0.5, Nickel - 0,08.

The ore is crushed to a particle size of 0 - 5 mm, mixed with coke in the ratio of ore : Cox = 4:1 and is sintered in a kiln at 750oC for the 0.8 PM Cooled to 100oC sintered material is ground in a mill wet grinding to a particle size less than 1 mm and treated in a sealed reactor 3,0 N abgaznaya hydrochloric acid containing 1.0 wt.% organically bound chlorine, at 85oC and T:W = 1:8 for 0.8 h, maintaining a pH of 1.0 with constant stirring of the reaction mixture.

The resulting slurry filtered. Traces of hydrochloric acid, the solid residue is directed to the use in construction.

From the solution to a temperature of 50oC precipitated hydroxides of iron, Nickel, cobalt, aluminum, and copper to establish a pH of 5.5. Filtered on a suction filter the precipitate hydroxides of impurity metals is washed with hot water. The precipitate be stacked for further processing.

The solution of chloride of manganese (II) is mixed under continuous stirring the air dissolve the exact solution, Rasulova in hot water, washed on a vacuum filter at T: W = 1:3, wring out the water on the filter and dried concentrate in a tumble dryer.

In the working area there are no pairs of hydrochloric acid.

The resulting concentrate contains manganese, wt.%: manganese is at least 60, iron - 0,7, silicon - 0,5, carbon - 0,05, p is less than 0.001, sulfur - 0,1, lead - less 0,0005, chlorine - 0,1.

The content of heavy metals (lead) is less than 0,0005%.

Received high manganese concentrate.

Extraction of manganese from ores is to 94.8%. The degree of enrichment of 4.1.

The results of the method in terms of industrial enterprises confirm:

1. The possibility of processing by the claimed method mn containing ores of different mineralogical composition, containing less than 30% of manganese, with the recovery in concentrate from ore not less than 95%.

2. The method allows to process mixed manganese ore without their enrichment to manganese concentrate with a concentration of from 2 to 6.

3. The content of manganese oxides in the target product of 94.8 wt.% and the amount of impurities is less than 5%.

4. The method can involve in the production otin.

6. There is no accumulation of industrial waste.

1. The method of processing of manganese ores, including the crushing ore, the translation into a solution of manganese and related impurities, the separation of the sludge, cleaning solution from impurities, the allocation concentrate manganese, followed by the separation from the mother liquor, filtering and drying, characterized in that the crushed ore is subjected to the combined roasting - baking carbon-based material at 600-900oAnd the ratio of reducing agent: ore=1:(1-6), spec process of 3.0-12 N abgaznaya hydrochloric acid containing 0.003 to 1.5 wt. % of organically bound chlorine in 70-95oS, and T:W=1:(1,5-8:0); in separated from the slurry solution was adjusted pH to 4.0 to 6.0, and produce a concentrate of manganese at 40-90oWith the introduction of the oxidizer solution to establish a pH of 7.6-14,0 separated from the mother liquor concentrate manganese washed with hot water at T:W=1:(2,5-3:5).

2. The method according to p. 1, characterized in that the primary ore is crushed to particle sizes 0-5 mm

3. The method according to p. 1, characterized in that the oxidation of Mn (II) conduct an oxidizer selected from the group of sodium hypochlorite, hydrogen peroxide, air or mixtures thereof.

4. The method according to p. 1, distinguishing the

 

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FIELD: metallurgy.

SUBSTANCE: manganese dioxide obtaining method involves dilution of manganese-containing raw material in nitric acid so that solution of manganese nitrates and nitrates of calcium, potassium, magnesium and sodium impurities contained in the ore is obtained. Then, thermal decomposition of nitrates in autoclave is performed. Thermal decomposition is performed at constant pressure drop in autoclave, starting from pressure of 0.6 MPa and reducing it to the end of the process to 0.15 MPa. At that, pulp is constantly mixed at thermal decomposition with the mixer rotating at speed of 1-15 rpm and with superimposition of vibration on it with frequency of 20-50 Hz. Method can be implemented at chemical plants provided with pressure autoclaves.

EFFECT: obtaining manganese dioxide of improved quality.

2 tbl, 2 ex

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