The method of processing the mn containing materials

 

(57) Abstract:

The invention relates to metallurgy manganese and can be used in the hydrometallurgical processing of vysokofosforistye carbonate and mixed manganese ores and concentrates, or waste, resulting in their physical enrichment for producing enriched low-phosphorus manganese concentrate required for the production of high-grade manganese alloys or direct alloying of steel. The method includes the preparation of pulp raw materials using working solutions, leaching of manganese hydrochloric acid, filtered to separate the filtrate from the residue obtained after leaching and leaching, precipitation of manganese from the filtrate suspension milk of lime, filtering, separating enriched in manganese concentrate from the mother liquor, subsequent washing with water and the process of evaporation of the mother liquor to obtain calcium chloride, washing the residue from the leaching spend part of the mother liquor, washing enriched manganese concentrate (OMC) is carried out in two stages. The method can significantly reduce the energy consumption for evaporation of the solution and, redlagaemyi method provides a comprehensive use of raw materials, since the release of two commercial products OMC and calcium chloride complex used all useful components introduced into the production cycle as manganese, calcium and hydrochloric acid. The proposed method also provides a waste-free technology with a significant reduction of water consumption and toxic discharges. 6 tab., 2 Il.

The invention relates to metallurgy manganese and can be used in the hydrometallurgical processing of vysokofosforistye carbonate and mixed manganese ores and concentrates, or waste, resulting in their physical enrichment for producing enriched low-phosphorus manganese concentrate required for the production of high-grade manganese alloys or direct alloying of steel.

The known method of chemical enrichment of oxide manganese ores (U.S. Pat. RF N 2038396, IPC C 22 B 47/0, prior. from 16.04.93), including crushing and grinding ore, leaching of manganese saturated solution of calcium chloride, separating the filtrate from the residue and precipitation of manganese from a solution of lime, while the leaching of lead by mixing the ore with a saturated solution x is JPY to 220-240oC-flow heater for 0,75-1,0 h, pumping through the battery autoclave, heated to 220-240oC, and then adding to the slurry of the iron chloride based obtain in the solution concentration of 7.5-9.0% of chloride of iron and pumping the slurry within 1-1 .5 h after the second battery autoclave, heated to 220-240oC. After leaching spend slurry cooling in counterflow heater up to 80-90oC, filtering and washing of the residue from the leaching of water and precipitation of manganese from the filtrate are lime pushonkoj. The solution during the deposition of the mixed blowing in the air, heated to 70-80oC.

The disadvantages of this method are the high energy costs (the two-stage leaching is carried out at 220-240oC), complex instrumentation (triple pumping through a battery of digesters: first, for heating and leaching in two stages, and then cooling the slurry), high vodosnabzhenie (need large amounts of water for washing of the final product from the salt, because the concentration of calcium chloride in the solution 450-490 g/l, and for cooling of the pulp after leaching with 220-240oC up to 80-90oC).

Most b is f N 1832736, IPC C 22 B 47/00, prior. from 3.04.90), in which the processing of crushed mn containing materials is carried out with hydrochloric acid in the presence of ferrous iron compounds by filing acid in aqueous suspension with a speed of 0.8-2.0 l/h per 1 kg of concentrate to a pH of 2.0 - 2.6 and extract with stirring, after exposure bringing the pH of the pulp to 2.9-3.2, filtration and washing of the residue from leaching using wash water to prepare slurry before the leaching of manganese on the next cycle. From the filtrate obtained after leaching of manganese, the addition of lime milk suspension lead deposition enriched in manganese concentrate (hereinafter OMC) at pH 10 for 0.5 hours the Precipitate is filtered off, washed with water, dried and calcined (Fig. 1)

The disadvantages of this method include:

the effluent in the form of industrial water;

- high water consumption for cooking pulp before leaching, lime milk, washing the OMC;

- high energy consumption for evaporation of solutions with low concentrations of chloride of calcium;

- loss of manganese and calcium chloride with drainage waters.

In the present invention are achieved by the following technical results:
organza with discharges;

- reduction of energy consumption for evaporation of solutions;

- the integrated use of raw materials and chemicals.

Technical results achieved by the fact that in the known method of processing the mn containing materials, comprising preparing a slurry of starting materials using working solutions, leaching of manganese hydrochloric acid, filtered to separate the filtrate from the residue obtained after leaching and leaching, precipitation of manganese from the filtrate suspension milk of lime, filtering, separating enriched in manganese concentrate from the mother liquor, subsequent washing with water and the process of evaporation of the mother liquor to obtain a powder of calcium chloride, leaching is carried out at a pH of 1.6 to 2.2, washing of the residue from the leaching spend part of the mother liquor at T:W = 1: (1,5-8) and a temperature of 20-50oC, directing all wash water for the preparation of lime milk, and washing the OMC is carried out in two stages, feeding for washing in the first stage part of the wash water at T: W = 1:(2-3) obtained at the second stage of leaching, while in the second stage leaching served water with a temperature of 20-80oC and T:W=1(6-8), while the remainder of the wash water after the second hundred of the target and the resulting working solution used for preparation of pulp raw materials. The remainder of the mother liquor is fed to evaporation to produce a marketable product powder of calcium chloride.

Process flow diagram of the prototype and the proposed method is shown in Fig. 1 and 2 (respectively).

Example 1.

To determine the optimal proportions of T:W when washing waste product experiments on leaching residue from leaching. For this purpose, 200 grams of the original carbonate manganese concentrate production Ordzhonikidze GOK (Ukraine), containing, wt.%: 30,2 Mn; 0,27 P; 9,45 SiO2; 123 CaO; 3,53 MgO; 2,29 Fe2O3; 8,6 C, held leaching of manganese by the following method: source material fraction minus 0,315 mm repulpable 0.15 l of water with a temperature of 70oC and introducing concentrated hydrochloric acid and 2 g/l of iron chloride (II), conducted leaching of manganese during mixing of the slurry over 4.5 CV at a pH of 1.7. The addition of hydrochloric acid is carried out with a speed of 0.8 - 2 l/H. Then adjust pH to 3.0 by the addition of lime milk suspension with the consumption of CaO 0.4 g/l, withstood the slurry under stirring for 30 minutes and filtered out the rest. Dividing it into two equal parts, spent washing in the layer at a temperature of 20The results of the experiments are given in table. 1.

From the results table. 1 shows that the optimal ratio of T:W when washing the residue is the ratio of T:W = 1,5 - 8,0.

With respect to T: W below 1.5 low degree of shading manganese, and consequently, a great loss with the residue, obtained by leaching. With increasing T:W over an 8.0 is a slight increase in the degree of shading, increased water consumption in the production cycle, and in addition, there is a dilution of the washing solution on the content of manganese.

Example 2.

Determination of the optimal temperature interval when washing the residue from the leaching is carried out according to the following procedure: from 300 g of the original carbonate manganese concentrate was videlacele manganese under conditions shown in example 1, was filtered and the obtained residue from leaching were divided into 7 parts. Then spent washing of the residue with repulpable at T:W= 1: 4 solution of calcium chloride with a concentration of 190 g/l, by setting a certain temperature of the pulp with active stirring. The residue was filtered, and determined the extent of washing of manganese (table. 2).

From the experimental results it follows that in the temperature range 20-50oC the degree of washout is.

Example 3.

To determine the effect of calcium chloride concentration in the filtrate - source solution prior to deposition of the OMC - on the content of calcium chloride in the mother solution, we performed a series of experiments according to the following procedure: to 0.2 l of chloride of manganese with manganese content of 60 g/l of added salt of calcium chloride to obtain the AC content in the initial solution and then added with stirring the milk of lime to pH 10.

After holding for 0.5 hours spent filtering, washing the precipitate OMC water and analysed the mother liquor content CaCl2and OMC after calcination at 750oC for 1 h on the manganese content.

The results of the experiments are given in table. 3.

From the experimental results it follows that within the initial concentration of calcium chloride from 120 to 350 g/l salt content in the mother solution after separation of the OMC increases from 180 to 252 g/L. However, a further increase in the initial concentration of up to 330 to 340 g/l leads to a decrease in the content of total manganese in OMC with 57,8 to 50.8% and drops sharply to 46.2% manganese, with its increase up to 350 g/L. This is due to the coprecipitation of calcium in the composition of the OMC, that reduces EGTA CA is calcium chloride before deposition should be at the level of 120-340 g/l, that provides a high concentration of calcium chloride in the mother solution, reducing energy consumption for evaporation in obtaining commercial product powder of calcium chloride and high quality OMC.

Example 4.

To determine the optimal settings of the first stage of leaching OMC to the filtrate obtained by the parameters specified in example 1 was added 220,8 g/l salt of calcium chloride, besieged manganese lime milk suspension on parameters given in example 3, and was filtered, separating the OMC from the mother liquor. The salt concentration in the mother solution was 200 g/l and humidity sediment 55 Rel.%.

To determine the optimum ratio of T:W wash divided nephropathy OMC into 12 equal parts of 15 g and held his flush repulpable in water and in a solution of calcium chloride with a concentration of 28.9 g/l at different relations T:railroad After stirring at 20oC for 1 h, filtered precipitation and lavage determined the salinity (salt content or C. S. - the amount of salts of calcium chloride (mostly) and magnesium determined during the process of evaporation of an aliquot of solutions to produce the balance of salts, dried at 105C and weighing) and loss of manganese from the solution.

Resultofthe solution containing calcium chloride, at T:W =1:(2-3,0), since the washing of water with the growth of T:W increases loss of manganese with a wash water from 0.28 to 0.47% in comparison with a wash by the present method with the 0.04 to 0.17% (i.e. less 7-2,8 times). With the increase of the ratio T:W 1:3,2 increases loss of manganese to 0.33 Rel.%, therefore, further improvement is impractical.

The benefits shown in the leaching solution of calcium chloride in comparison, using for this purpose the water, allow the proposed method to use on the first stage of leaching OMC wash water obtained in the second stage of leaching, which allows to increase the salt concentration in the wash water output from the first stage, from 56.4 - 38,9 to 100,2 - 85,6 g/l When used in the composition of the working solution at the stage of leaching and subsequent deposition OMK this gives the opportunity to increase the salt concentration in the mother solution, shown on the process of evaporation, and hence to reduce the energy consumption to receive commodity powdered calcium chloride.

Use at the first stage of province OMC wash water obtained from the second stage, and its subsequent use in the composition of the working solution, supplied with prigotovleniya, containing mn containing toxic compounds and, ultimately, to reduce the loss of manganese.

Example 5.

For comparison, the specific water consumption discharge generated in the technological cycle, the prototype and the proposed method has conducted a series of experiments whose results are shown in table. 5.

For these purposes, in each experiment a sample of 50 g of a source of manganese concentrate, obtained during the concentration of carbonate manganese ore Midnight field (RF) containing, wt.%: 27,03 Mn; 0,21 P; 18,7 SiO2; 4,63 CaO; 1,67 MgO; 5,9 Fe2O3; 24,6 loss during annealing, the fraction minus 0,315 mm, repulpable at T:W = 1:5 in 0.25 l and processed for extraction of manganese on the conditions described in example 1. Then were filtered to separate the filtrate from the rest. The residue was washed with T:W=1:7, and the temperature of the leaching solution 40oC. zero In experiments 1 and 3 (table. 5) washing was performed with water, and in experiment 2 under the terms of the prototype the entire volume of wash water - 0,116 l is directed to the preparation of the slurry to leaching, while reducing water consumption from 0.25 l to 0,134 L.

To experiment the proposed method was also conducted oliveriana are given in table. 5 (experiment 3 and 4). In the cycle of the proposed method (experiment 4) for leaching residue from the leaching filed 0,116 l mother liquor obtained in the zero cycle, due to which the consumption is zero. All wash water obtained at this stage (0,116 l), was directed to the preparation of known milk, which was used for deposition of the OMC from the filtrate, therefore discharges equal to zero. After separation of the mother liquor from the OMC, the sediment washed in two stages: the first stage at T:W = 1:3 and used 0,072 l washing solution from the second stage of leaching from zero and in the second stage - water at T:W = 1: 7 and use has 0.168 l of water with a temperature of 70oC. Thus, at this stage will be used just has 0.168 l of water. For making pulp source material was used 0.25 l of working solution consisting of the total volume (0,072 l) wash water obtained after the first stage of leaching OMC, has 0.168 residue of wash water after the second stage of leaching OMC and 0,082 l (i.e., up to 100%) added to the mother liquor. Thus, in the preparation of pulp for leaching water was zero, the discharge was completely absent.

The terms of the specific indicators in l/kg initial conc the beam receiving condensate from evaporation of the mother liquor consumption is almost completely will be zero, to reduce operational energy and labor for processing the source material to get the OMC and powder CaCl2and to ensure the integrated use of raw materials, because commodity products goes manganese, calcium from raw materials and chlorine ions from the hydrochloric acid.

Example 6.

On the basis of the performed experiments experiments on full-cycle technology for obtaining high-manganese concentrates (OMC) in the processing of the mn containing materials using working solutions of the proposed method.

In this case, used the concentrate of dry beneficiation of manganese ore Nicholas Deposit (Ukraine), containing, wt.%: 29,5 Mn; 0,27 P; 9,45 SiO2; 12,3 CaO; 3,53 MgO; 2,29 Fe2O3; 8,6 C.

Getting the OMC was performed according to the scheme shown in Fig. 2: sample source of manganese concentrate in the amount of 1000 g of fraction minus 0.4 mm in zero cycle (experiment 1) to prepare a slurry of the starting material with the addition of water with respect to T:W = 1:3,25 and perform the leaching of manganese with the introduction of hydrochloric acid to a pH of 1.6 when paramasivan according to the method described in example 1. Then spent filtration and the residue from the leaching of prom is the service suspension milk of lime at zero cycle used water, having the concentration of calcium oxide 150 g/l) manganese concentration 14.1 g/l was directed to the preparation of suspensions of known milk for the deposition of manganese on the proposed method, receiving the CaO concentration of 150 g/l On the second, third and the following cycles for the preparation of suspensions with the same concentration of CaO used wash water from washing the residue, obtained by leaching.

In the filtrate, containing 70,5 g/l of manganese was added to a suspension of lime milk to a pH of 10.0 and precipitated manganese under stirring for 30 minutes. Then spent filtering and zero cycle obtained OMC washed in two stages water, using it at a temperature of 60oC T:W = 1:3.0 in the first stage and the at T:W = 1:6 in the second stage.

At the first stage of leaching got the wash water with a salt content of 112.8 g/l, on the second - to 43.1 g/L.

Wash water from the second stage of leaching at T:W = 1:3,0 sent to the first stage of the first washing cycle carried out by the proposed method and the balance after the merger with the wash water obtained in the first stage of leaching, and the addition of up to 100% of the mother liquor (filtrate after separation of the OMC) was sent to prepare the slurry source Marganets is for OMC, conducted 32 experience. After the seventh cycle the system has come to equilibrium in the future were obtained stable results, therefore, in the table. 6 shows the results for the zero, eighth, twenty-second and thirty-second experiments. The experimental results show that the washing water, the resulting on-stage leaching residue from the leaching of contents 14.1 to 14.9 g/l of manganese or about 12% manganese, from entrants in the technological cycle, the present method is directed to the preparation of lime milk. This technique reduces the losses of manganese in comparison with the prototype, so to free from impurities, the solution comes immediately to obtain the desired product of the GCF. This allows you to have as part of the suspension embryos mn containing phase, which then allow almost completely with great speed for 30 min precipitate the manganese to a residual content 0,19 - 0,007 g/l, reducing the loss of manganese.

The turnover of this solution again on stage leaching (method prototype) would be inappropriate. This is due to the fact that upon contact of the solution with the feedstock may increase the pH at the interface of solid particles with the surface that will lead to insoluble connected to the cutting stage technologies: repulpable, leaching of manganese, filtering to separate from the rest and re-enter on the stage of washing.

The turnover of solutions for the proposed method (Fig. 2) allows to increase the salt concentration in the mother solution with 112,8 to 216,3 g/l and to reduce the energy consumption for evaporation of the solution in order to obtain a marketable product powder of calcium chloride, about twice. The content of manganese in the main commercial product of the GCF is at a high level: in a dry OMC (drying to constant weight at 105oC) its content varies within 57,4 - 59,6%, and taking into account losses during annealing (extract 1 h at 850oC) this value rises to 61.5-68,11%. Such manganese content exceeds all the best grades of manganese ores of metallurgical grade, available on the world market.

When washing the OMC with respect to T:W=1:3 for the proposed method obtained in the wash water after the 1st stage salinity from 43,1 up for 125.8 g/l due to the use of wash water with a temperature of 40oC, with salinity from 21,65 to 38.1 g/l 2nd stage leaching OMC poured water with a temperature of 70oC and the ratio of T:W = 1:6. From the obtained volume of wash water in the second stage, half were sent to stage 1 about the Oh water from 1 stage of leaching OMC and additive stock solution to 100%. Working solution used in the preparation of pulp source of manganese material before leaching of manganese on the next cycle. Thus, on evaporation to obtain the chloride of calcium intake 60% stock solution with high concentration 216,4 - 226,3 g/l of salt and 0.007-0,009 g/l of manganese provided: reduction of energy consumption for evaporation of the solution, reduction of losses of manganese 0.2 - 0.02% of the introduced loop with mn containing source material and complex use of raw materials, because the release of two commercial products OMC and calcium chloride in them comprehensively used all useful components introduced into the production cycle as manganese, calcium and hydrochloric acid. In addition, the proposed method provides a waste-free technology with a significant reduction of water consumption and toxic discharges.

The method of processing the mn containing materials, comprising preparing a slurry of starting materials using working solutions, leaching of manganese hydrochloric acid, filtered to separate the filtrate from the residue obtained after leaching and leaching, precipitation of manganese from the filtrate suspension milk of lime, filerecoveryangel the mother liquor to obtain a powder of calcium chloride, characterized in that the leaching is carried out at a pH of 1.6 to 2.2, washing of the residue from the leaching spend part of the mother liquor at T : W = 1 : (1,5-8) with a temperature of 20-50C, directing all wash water for the preparation of lime milk, and wash enriched manganese concentrate is carried out in two stages, feeding for washing in the first stage part of the wash water at T : W = 1 : (2-3) obtained at the second stage of leaching, and in the second stage of the washing water is supplied with a temperature of 20 to 80C and at T : W = 1 : (6-8), while the remainder of the wash water after the second stage combined with the wash water obtained after the first stage of leaching add up to 100% of the mother liquor and the resulting working solution used to prepare the slurry of starting materials, and the remainder of the mother liquor is fed to evaporation.

 

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