CN109939832B - Manganese ore enrichment method combining selection and smelting - Google Patents
Manganese ore enrichment method combining selection and smelting Download PDFInfo
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Abstract
The invention discloses a manganese ore enrichment method combining selection and metallurgy, which comprises the following steps: (1) mixing and grinding water and manganese ore to prepare manganese ore pulp; (2) mixing the manganese ore pulp with a leaching agent, controlling the pH value of the manganese ore pulp to be 3-5.5, leaching, and separating to obtain manganese middlings and a leaching solution; (3) carrying out reverse flotation desilicification on the manganese middling to obtain ferromanganese concentrate; (4) adding regenerants of quicklime and sulfuric acid into the leachate in sequence to obtain a regenerated leaching agent, returning the regenerated leaching agent to the step (2) for use, and selling magnesium hydroxide and calcium sulfate for sale. The manganese enrichment method has the advantages of short flow, no sewage and waste residue discharge, no need of heating or pressurizing equipment, low corrosion prevention requirement on equipment, safe production, greenness and environmental protection, and can realize the step-by-step extraction of manganese, iron, calcium and silicon.
Description
Technical Field
The invention discloses a manganese ore enrichment method combining the dressing and smelting of manganese ore, particularly ferromanganese ore and tailings of magnetic separation manganese ore, belongs to the field of mineral processing in chemical metallurgy, and particularly relates to a manganese ore dressing and chemical combination enrichment method.
Background
China has rich manganese resource reserves, but the grades are not high, the contents of silicon, aluminum, iron and calcium ores are high, manganese belongs to iron group elements, the content of manganese accounts for about 0.1 percent of the earth crust, and the physical and chemical properties of manganese are similar to those of iron. Manganese is distributed in nature in various compounds.
Manganese-based alloys are important raw materials essential in the steel industry, and manganese is also used for producing manganese metal, manganese alloys and manganese compounds and is widely applied to the aspects of industry, agriculture, military affairs and the like. China is a country with poor manganese resources, the self-supply quantity of the manganese resources is seriously insufficient, most of manganese resources are poor manganese ores and manganese-rich ores account for less than 10 percent of the total reserves in terms of the yield and reserves of the manganese ores in China. Therefore, research on comprehensive utilization of low-lean manganese ore resources is more and more important, and the comprehensive recovery of manganese ore dressing tailings and low-lean manganese resources plays an active role in economic construction.
Manganese ores are classified into manganese carbonate ores, manganese oxide ores, mixed ores and multi-metal ores according to the natural type of the ore and associated elements contained in the ore. Although the types of manganese ores are more, the basic ore dressing method is similar to that of weak magnetic iron ores, and the method is characterized in that the ore dressing method is more and is used in combination, but the enrichment ratio is low and the recovery rate is not high; another feature of manganese ore beneficiation is size fraction beneficiation to obtain concentrates of different size fractions. In order to improve the sorting index, coarse fraction magnetic separation after desliming is carried out, medium fraction gravity separation is carried out, and fine fraction flotation is carried out, so that separation of manganese ore and gangue or extraction of associated elements is realized, and the production cost is reduced.
The types of manganese ores in China are mainly carbonate manganese ores, and account for about 73 percent of the total reserves. The ore has low grade, the general manganese grade is below 20 percent, the ore belongs to marine sedimentary type and sedimentary metamorphic type manganese ore beds, the reserve capacity is about 40000 ten thousand tons, and the ore is mainly distributed in Yunnan, Sichuan, Hunan, Hubei, Guangxi and the like.
Manganese ore has the characteristics of low hardness, brittleness and the like, so that the manganese ore is easy to argillize in the processes of mining, transporting and crushing. The beneficiation method is different according to the type of manganese ore. At present, the conventional mineral separation methods such as gravity separation, magnetic separation, flotation and the like cannot obtain good production and operation effects, and the purposes of resource saving and environmental friendliness are more difficult to achieve.
The extraction of manganese from manganese-containing raw materials by hydrometallurgical methods has been studied since the end of the nineteenth century. However, the research direction is mostly to leach and extract manganese, and mainly comprises the steps of selecting appropriate chemical raw materials to convert manganese in ores into soluble forms, enabling the soluble forms to enter a solution, separating the soluble forms from gangue minerals, purifying the solution to remove impurities such as Fe, Al, Si, P, Cu and the like dissolved together with the manganese, and finally preparing required manganese products such as electrolytic manganese, manganese oxide, various manganese salts and the like by methods such as electrodeposition, precipitation or crystallization. However, the methods have the defects of long flow, difficult operation, high cost and the like, and are not suitable for low-grade manganese ores with the manganese content of less than 10 percent. No successful example is available for the beneficiation of low-grade, low-grade lean manganese ores, mainly of manganite or ferromanganese ores.
The semi-manganese oxide ore, the hard manganese ore and the ferro-manganese ore are typical complex and difficult-to-treat manganese ores, the cause of the manganese ore deposit of the ores generally belongs to a deposition type or deposition modification type ore deposit, calcium, magnesium, iron impurities and the like are similarly like fine particles which are impregnated in the manganese ores, the manganese ore deposit has the characteristics of fine embedded particle size, complex symbiotic relationship and the like, and even if a monomer is dissociated, ore grinding is carried out below 5-10 mu m, so that the difficulty of mineral separation is increased, and the separation is difficult by a method of magnetic separation, gravity separation and flotation combined ore dressing. Therefore, only the key technology of refractory manganese ore is developed, and the high-value utilization of the resources can be realized.
The literature "research on recycling of low-grade manganese carbonate ores" refers to a method for treating low-grade manganese ores, namely, raw ores containing 8.11% of Mnand 3.41% of Fes are treated by a sulfuric acid leaching method, and the experimental conditions are optimized to meet the requirements on product quality; the literature 'research on treating low-grade ferromanganese ore by magnetizing, reducing and roasting' refers to a method for treating low-grade manganese ore, wherein ferromanganese ore containing 30-45% of Fe and 7-15% of Mn is subjected to reducing roasting in a reducing atmosphere under a certain temperature system, and roasted materials are leached by sulfuric acid; the methods mentioned in the literature "research on recycling of low-grade manganese carbonate ore" and "research on treating low-grade manganese iron ore by magnetizing reduction roasting" both use sulfuric acid leaching. The methods have complex processes and high requirements on equipment corrosion resistance; the manganese-containing liquid leached by sulfuric acid has high impurity content, and the cost of the subsequent process is increased.
The patent (application number CN200710062305.5) discloses a method for treating low-grade manganese ore powder, which is to directly prepare low-carbon metal ferromanganese from poor manganese ore powder through raw material selection, crushing, fine grinding, sieving, mixing, stirring, microwave oven preheating, carbon monoxide prereduction, final reduction, high-temperature refining, nitrogen cooling protection and magnetic separation purification. The method has long process flow, needs high temperature and microwave heating and special gas reduction and protection, and is difficult to be industrially applied.
The patent (application number CN200810143103.8) discloses a beneficiation method of low-grade manganese carbonate ore, which is to grind raw material ore into powder, add water to prepare ore pulp, add a medicament in proportion under a certain pH value, and perform closed cycle flotation. The recovery rate of manganese in the method can reach 85%, but the flotation enrichment ratio is only 1.5, and high-grade manganese ore cannot be obtained.
The patent (application number CN201010300557.9) discloses a beneficiation method of low-grade manganese carbonate ore, and the technical scheme of the invention is characterized in that: by adopting a coarse and fine grading coarse grain magnetic separation fine grain flotation recovery process, the manganese magnetic concentrate and the manganese flotation concentrate with the grade of 26% can be obtained step by 18%, so that the comprehensive recovery rate of 8% low-grade manganese carbonate ore can reach more than 80%, but the actual recovery rate is not high, and the high-grade manganese concentrate is difficult to obtain.
The patent (application number CN201110300784.6) discloses a method for preparing manganese-iron alloy from low-grade manganese ore, which comprises the steps of drying the low-grade manganese ore with the content of manganese metal of 15-30%, adding a reducing agent, a catalyst, a flux and a binder, uniformly mixing, putting the composite raw material into a rotary kiln or a tunnel kiln, taking coal gas or natural gas as an energy source, keeping the weak reducing atmosphere in the kiln, reacting under a certain temperature system, cooling and magnetically separating the reacted material to obtain the manganese-iron alloy and tailings. The method also needs kiln equipment for high-temperature reduction, has large energy consumption and high cost, and the ferromanganese alloy obtained by magnetic separation cannot meet the requirements of relevant standards.
The patent (application number CN201510413971.3) discloses a beneficiation method of low-lean manganese ore with high silicon associated with a small amount of limonite and psilomelane, which has simple process, limited application range and low recovery rate.
The patent (application number CN201710687368.3) discloses a method for synchronously recycling manganese and iron in low-grade manganese carbonate ore, which essentially comprises the steps of leaching by sulfuric acid and precipitating iron from a manganese sulfate solution by ammonioiarosite. The method can solve the problem of high iron content in the sulfuric leachate in the low-grade manganese carbonate ore, but reduces the utilization value of iron relative to manganese-based alloy, and still needs other procedures to remove other impurities in the leachate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a manganese enrichment method combining concentration and metallurgy, which has the advantages of short flow, no sewage and waste residue discharge, no need of heating or pressurizing equipment, low corrosion prevention requirement on equipment, safe production, environmental protection and capability of realizing the step-by-step extraction of manganese, iron, calcium and silicon.
In order to achieve the purpose, the invention provides a manganese ore enrichment method combining smelting and dressing, which comprises the following steps:
(1) mixing and grinding water and manganese ore to prepare manganese ore pulp;
(2) mixing the manganese ore pulp with a leaching agent, controlling the pH value of the manganese ore pulp to be 3-5.5, leaching, and separating to obtain a leaching solution and a manganese middling;
(3) performing reverse flotation desilicification on the manganese middling to obtain flotation froth concentrate as silicon concentrate, and underflow tailings as ferromanganese concentrate;
(4) adding regenerants of quicklime and sulfuric acid into the leachate in sequence to obtain a regenerated leaching agent, returning the regenerated leaching agent to the step (2) for use, and selling magnesium hydroxide and calcium sulfate for sale.
Preferably, the manganese ore is at least one of pyrolusite, psilomelane, hausmannite, rhodochrosite, psilomelane, manganite, manganosite and mangnesite; more preferably at least one of rhodochrosite, calciumusite and manganese calcite.
Preferably, in the step (1), the liquid-solid weight ratio of the water to the manganese ore is 2-6: 1; more preferably, the liquid-solid weight ratio of the water to the manganese ore is 3-5: 1.
Preferably, in the step (1), manganese ore and water are ground and mixed to prepare manganese ore pulp, wherein the granularity is larger than or equal to 70% of-74 microns; more preferably, the particle size is-74 μm at a ratio of 80% to 90%.
Preferably, in the step (2), the pH value is 4.5-5.5. The inventors have found that the overall recovery of manganese and the grade of manganese in ferromanganese concentrates can be further improved within the preferred ranges of the invention.
Preferably, in the step (2), the leaching agent is 1-10 wt% of hydrochloric acid; more preferably 5 to 8 wt% of hydrochloric acid. The invention skillfully controls the leaching pH value under the condition of leaching dilute hydrochloric acid, preferentially leaches the carbonate of calcium and magnesium, the leaching rate of manganese, iron, silicon and the like in manganese ore is less than 5 percent, and the calcium carbonate and the magnesium carbonate preferentially react with a leaching agent as follows:
CaCO3+2HCl＝CaCl2+H2O+CO2
MgCO3+2HCl＝MgCl2+H2O+CO2
the enriched manganese middling is obtained after the reaction, the cementing effect of carbonate in manganese ore and other minerals (quartz, mica, limonite and the like) is dissolved, and the separate flotation of other minerals becomes possible.
Under the condition of dilute hydrochloric acid leaching, the pH value of leaching needs to be strictly controlled, and when the pH value is too low, manganese is dissolved out and enters a leaching solution, so that the loss of manganese is generated; when the pH value is too high, the calcium and magnesium are not completely dissolved out, the silicate minerals and the manganese minerals are difficult to dissociate, and the recovery rate and grade of the subsequent manganese flotation are reduced.
Preferably, in the step (3), the reverse flotation conditions are as follows: the liquid-solid weight ratio of water to the manganese middlings is 3-8: 1, the pH value is 7-11, the flotation reagent is one or a combination of C12-C18 alkyl primary amine salts, and the dosage is 20-500 g/ton.
Preferably, in step (4), Ca in the leaching agent is regenerated2+Concentration not less than 0.5g/L, Mg2+The concentration is not less than 0.2 g/L. The leachate regeneration process of the invention has the following reactions:
MgCl2+Ca(OH)2＝Mg(OH)2↓+CaCl2
CaCl2+H2SO4＝CaSO4↓+2HCl
in the implementation of the step, the inventor researches and discovers that Mg2+When the concentration is less than 0.2g/L, the use amount of lime and sulfuric acid is increased, so that the preparation cost is increased; ca2+When the concentration is less than 0.5g/L, the use amount of sulfuric acid is increased, and sulfuric acid exists in the regenerated leaching agent, so that calcium sulfate colloid is generated on the surfaces of mineral particles in the leaching process in the step (2), and the leaching effect is influenced.
Preferably, after the steps are carried out, the total recovery rate of manganese is 90-95%, and the mass content of manganese in the ferromanganese concentrate is 25-35%.
According to the invention, through the processes of grinding, leaching, reverse flotation and leaching regeneration, manganese ore is firstly prepared into manganese ore pulp; under the condition of strictly controlling pH, the manganese ore pulp is leached by a dilute hydrochloric acid leaching agent to preferentially leach calcium and magnesium carbonates, and the leaching rate of manganese, iron, silicon and the like in manganese ore is less than 5 percent, so that manganese middlings and leachate are obtained by leaching; performing reverse flotation on the manganese middling to obtain silicon concentrate and ferromanganese concentrate; the leachate is subjected to leaching regeneration, the obtained regenerated leaching agent is returned to the manganese ore pulp for leaching, and the obtained byproducts such as magnesium hydroxide, gypsum and the like can be directly sold after dehydration. The process of the invention achieves the purposes of comprehensively utilizing various valuable components in the raw ore and improving the economic value, and the extraction process basically has no solid waste discharge, thereby being a new green dressing and smelting technology.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the enrichment process of a manganese ore magnetic separation method, the recovery rates of manganese and iron are both improved by more than 20 percent.
(2) Compared with the enrichment process by a manganese ore flotation method, the process realizes the step-by-step extraction of manganese, iron, calcium and silicon.
(3) Compared with the enrichment process of manganese ore by gravity separation, the enrichment ratio is improved by more than 50 percent.
(4) Compared with a manganese hydrometallurgy process, the method has the advantages of short flow, safe production, no need of heating or pressurizing equipment and low corrosion prevention requirement on the equipment.
(5) Under the condition of low-concentration hydrochloric acid leaching, the invention preferentially leaches the carbonates of calcium and magnesium, and decomposes the cementation of the carbonates in manganese ore and other minerals (quartz, mica, limonite and the like), so that the separate flotation of other minerals becomes possible.
(6) The invention utilizes low-value sulfuric acid, lime and the like to remove impurities, realizes the regeneration and the cyclic utilization of the leaching agent, and further realizes the purpose of no sewage discharge.
(7) The method enriches manganese and iron, simultaneously extracts calcium, magnesium and silicon as byproducts step by step, basically has no solid waste discharge, and is a new green dressing and smelting technology.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
the refractory manganese ore comprises the following chemical components in percentage by mass:
TABLE 1 results of multielement analysis of manganese ores%
| Mn | TFe | P | SiO2 | MgO | CaO | Al2O3 | Burn and relieve |
| 14.89 | 2.65 | 0.16 | 4.79 | 4.82 | 32.67 | 0.35 | 31.58 |
(1) Crushing ores, adding water, and performing ball milling to obtain manganese ore pulp with the particle size of-74 mu m accounting for 85.3% and the liquid-solid ratio of 3;
(2) adding the manganese ore pulp into a stirring barrel, uniformly adding a leaching agent with the mass concentration of 6% HCl under stirring at 300r/min, keeping the pH value of the ore pulp at 4.5-5.5, and leaching for 3 hours to obtain leached slurry;
(3) precipitating the leached slurry for 1 hour, discharging the upper leachate, and taking manganese middling at the bottom;
(4) washing the bottom manganese middling with clear water for 3 times, dehydrating and drying to obtain dry manganese middling, and analyzing leaching rates of various elements in the dry manganese middling as follows: 2.62 percent of Mn, 3.54 percent of Fe, 92.3 percent of Ca and 90.6 percent of Mg; the grade of the dry manganese middlings is analyzed to be 35.6 percent of Mn, and the manganese concentrate grade can be achieved without flotation.
Example 2
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
the manganese ore magnetic separation manganese ore tailings prepared from the manganese ore through the construction of the Yunnan province comprise the following chemical components in percentage by mass:
TABLE 2 results of multielement analysis of raw ore%
| Mn | TFe | P | SiO2 | MgO | CaO | Al2O3 | Burn and relieve |
| 9.81 | 3.15 | 0.14 | 15.16 | 5.12 | 30.09 | 0.35 | 32.10 |
(1) Crushing and grinding the ore to obtain manganese ore pulp with the granularity of 74 mu m accounting for 86.0 percent and the liquid-solid ratio of 3;
(2) adding the manganese ore pulp into a stirring tank, uniformly adding a leaching agent with the mass concentration of 3.5% HCl under stirring at 300r/min, controlling the pH value of the ore pulp to be 4.5-5.0, and leaching for 3 hours at normal temperature to obtain leached slurry;
(3) centrifugally dewatering the leached slurry to obtain a solid manganese middling;
(4) washing the manganese middlings with clear water for 3 times, dehydrating and drying, detecting the yield and the contents of calcium, magnesium and manganese of the manganese middlings, and calculating the recovery rate as follows:
TABLE 3 leaching effect at pH 4.5-5.0%
(5) Mixing the manganese middling with clear water until the liquid-solid ratio is 4 to prepare flotation slurry;
(6) adding the flotation slurry into a flotation machine, and using NaCO3Adjusting pH to 9.5-10.0;
(7) with dodecylamine acetate: dodecyl trimethyl ammonium chloride ═ 1: 1 is collecting agent, the dosage is 350 g per ton ore, reverse flotation is carried out according to 4 rough 1 sweeps, the obtained foam concentrate is silicon concentrate, the component of the foam concentrate is analyzed, and SiO2The content is 75.1 percent, and the calculated recovery rate is 82.6 percent;
(8) and (3) dehydrating the flotation underflow to obtain ferromanganese concentrate, analyzing the content of Mn in the ferromanganese concentrate to be 26.6 percent and TFe to be 9.1 percent, and calculating the metal recovery rates to be Mn 93.0 percent and Fe 93.6 percent.
Example 3
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
a selection-smelting combined enrichment test is carried out on certain low-grade manganese ore in Hunan West of Hunan province. The Mn content of the mineral is 10.15%, and the gangue mineral mainly comprises silicate mineral and quartz, and comprises the following components in parts by mass:
TABLE 6 results of multielement analysis of manganese ores%
| SiO2 | Al2O3 | MgO | CaO | P | Mn | Pb | Ni | Fe | Cu |
| 38.52 | 10.69 | 1.65 | 6.01 | 0.18 | 10.15 | 0.021 | 0.011 | 0.041 | 0.0027 |
(1) Crushing and grinding low-grade manganese ore to-0.074 mm which accounts for more than 80%, and mixing ore pulp with clear water until the liquid-solid ratio is 4;
(2) will be provided withAdding the manganese ore slurry into a stirring barrel, and stirring at 400 r.min1Uniformly adding a leaching agent with the mass concentration of 3.8% HCl while stirring, keeping the pH value of the ore pulp at 5.0-5.5, and leaching for 4 hours at normal temperature to obtain leached slurry;
(3) vacuum filtering the leached slurry, wherein the filtrate is a leaching solution, and the filter cake is manganese middling;
(4) washing the manganese middling with clear water for 3 times, and then mixing the manganese middling with clear water until the liquid-solid ratio is 3 to prepare flotation slurry;
(5) adding the flotation slurry into a flotation machine, and adjusting the pH value to 9-10 by using NaOH;
(6) and (3) carrying out flotation according to 3 rough 1 sweeps by using laurylamine hydrochloride as a collecting agent with the dosage of 250 g per ton of ore quantity to obtain the foam concentrate, namely the silicon concentrate. Analysis of its composition, SiO2The content is 81.6 percent, and the calculated recovery rate is 80.5 percent;
(7) and (3) dehydrating the flotation underflow to obtain manganese concentrate, analyzing the manganese concentrate to contain 31.9% of Mn, and calculating the metal recovery rate to be Mn 91.7%.
Example 4
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
a manganese enrichment test combining the selection and smelting of certain poor iron manganese ores in Yunnan is carried out. The Mn content in the mineral is 15.6%, and the gangue mineral mainly comprises silicate mineral and quartz, and comprises the following components by mass:
TABLE 7 results of multielement analysis of manganese ores%
| SiO2 | Mn | TFe | Al2O3 | CaO | MgO | K2O | Na2O |
| 32.0 | 15.6 | 23.4 | 5.5 | 6.5 | 0.4 | 1.5 | 0.04 |
In addition, from the aspect of phase analysis, the manganese in the ore sample has only a very small amount of manganese carbonate, wherein most of the manganese carbonate exists in the form of pyrolusite, manganosite and ferromanganese compound minerals; phase analysis of iron shows that iron is mainly present as hematite, limonite. Multiple institutional researches show that the conventional magnetic separation, gravity separation and flotation have almost no separation effect on the ore, and the ore sample belongs to the extremely difficult-to-separate ferromanganese ore.
(1) Adding water into low-grade manganese ore, and carrying out ball milling to obtain manganese ore slurry with the particle size of-0.074 mm accounting for 85.6% and the liquid-solid ratio of 4;
(2) adding the manganese ore slurry into a stirring barrel, and stirring at 500 r.min-1Uniformly adding a leaching agent with the mass concentration of 4.1% HCl while stirring, keeping the pH value of the ore pulp at 4.5-5.0, and leaching for 4 hours at normal temperature to obtain leached slurry;
(3) vacuum filtering the leached slurry, wherein the filtrate is a leaching solution, and the filter cake is manganese middling;
(4) mixing the manganese middling with clear water until the liquid-solid ratio is 4 to prepare flotation slurry;
(5) adding the flotation slurry into a flotation machine, and using NaCO3Adjusting the pH value to 9-9.5;
(6) dodecyl amine hydrochloride: octadecylamine acetate ═ 2: 1 is collecting agent, the dosage is 350 g per ton ore, flotation is carried out according to 3 rough 1 sweeps, the obtained foam concentrate is silicon concentrate, the component of the foam concentrate is analyzed, and SiO2The content is 79.1 percent, and the calculated recovery rate is 81.8 percent;
(7) and (3) dehydrating the flotation underflow to obtain ferromanganese concentrate, analyzing the content of Mn in the ferromanganese concentrate to be 30.6 percent and TFe to be 42.1 percent, and calculating the metal recovery rates to be Mn 91.7 percent and Fe 93.0 percent.
Example 5
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
1 liter of the leachate obtained in example 1 was taken and analyzed for its ion concentration: ca2+36.1g/L, Mg2+It was 5.2 g/L.
Stirring the leachate, adding 15 g of quicklime powder at the speed of 1g per minute, and continuing stirring for 30 minutes after the completion to obtain a magnesium precipitation solution;
precipitating the magnesium precipitation solution, clarifying for 90 min, discharging supernatant, and testing Mg2+The concentration is 0.28 g/L; washing the bottom precipitate with clear water for 2 times, and dehydrating to obtain magnesium hydroxide.
Continuously and evenly dripping 200 g of sulfuric acid with the mass concentration of 50% into the magnesium precipitation clear liquid under the stirring condition, and continuously stirring for 30 minutes after finishing dripping of the sulfuric acid to obtain a calcium precipitation liquid;
precipitating the calcium precipitation solution, clarifying for 60 min, discharging supernatant, and testing Ca content2+0.57 g/L; washing the bottom precipitate with clear water for 2 times, and dehydrating to obtain calcium sulfate (Gypsum Fibrosum).
The obtained clear solution of precipitated calcium is the regenerated leaching agent.
Comparative example 1
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
(a) taking the manganese ore pulp obtained in the step (1) in the example 2.
(b) Adding the manganese ore pulp into a stirring tank, uniformly adding a leaching agent with the mass concentration of 3.9% HCl under stirring at 300r/min, controlling the pH value of the ore pulp to be 1.5-2.0, and leaching for 3 hours at normal temperature to obtain leached slurry;
(c) centrifugally dewatering the leached slurry to obtain a solid manganese middling;
(d) washing the manganese middlings with clear water for 3 times, dehydrating and drying, detecting the yield and the contents of calcium, magnesium and manganese of the manganese middlings, and respectively calculating the recovery rates as follows:
TABLE 4 leaching effect at pH 1.5-2.0%
It can be seen from the above table that the leaching pH was too low, which resulted in a reduction in the manganese middling metal recovery to 87.3%.
(e) Mixing the manganese middling with clear water until the liquid-solid ratio is 4 to prepare flotation slurry;
(f) adding the flotation slurry into a flotation machine, and using NaCO3Adjusting pH to 9.5-10.0;
(g) with dodecylamine acetate: dodecyl trimethyl ammonium chloride ═ 1: 1 is collecting agent, the dosage is 350 g per ton ore, reverse flotation is carried out according to 4 rough 1 sweeps, the obtained foam concentrate is silicon concentrate, the component of the foam concentrate is analyzed, and SiO2The content is 82.2 percent, and the calculated recovery rate is 84.6 percent;
(h) and dehydrating the flotation underflow to obtain the ferromanganese concentrate. The ferromanganese concentrate containing 27.0% of Mn and 9.5% of TFe was analyzed, and the metal recovery rates calculated were Mn 81.2% and Fe 90.2%.
In this example, the concentrate grade obtained by leaching at low pH was substantially equal to that of example 2, but the ferromanganese recovery was significantly lower than that of example 2(Mn 93.0%, fe 93.6%).
Comparative example 2
A manganese ore enrichment method combining selection and metallurgy specifically comprises the following operations:
(a) taking the manganese ore pulp obtained in the step (1) in the example 2.
(b) Adding the manganese ore pulp into a stirring tank, uniformly adding a leaching agent with the mass concentration of 3.5% HCl under stirring at 300r/min, controlling the pH value of the ore pulp to be 6.0-6.5, and leaching for 3 hours at normal temperature to obtain leached slurry;
(c) centrifugally dewatering the leached slurry to obtain a solid manganese middling;
(d) washing the manganese middlings with clear water for 3 times, dehydrating and drying, detecting the yield and the contents of calcium, magnesium and manganese of the manganese middlings, and calculating the recovery rate as follows:
table 5 leaching effect at pH 6.0-6.5%
As can be seen from the table above, due to the over-high pH value of leaching, the contents of MgO and CaO in the manganese middling are high, the leaching rate of MgO is only 46.3% and the leaching rate of CaO is only 56.8%.
(e) Mixing the manganese middling with clear water until the liquid-solid ratio is 4 to prepare flotation slurry;
(f) adding the flotation slurry into a flotation machine, and using NaCO3Adjusting pH to 9.5-10.0;
(g) with dodecylamine acetate: dodecyl trimethyl ammonium chloride ═ 1: 1 is collecting agent, the dosage is 350 g per ton ore, reverse flotation is carried out according to 4 rough 1 sweeps, the obtained foam concentrate is silicon concentrate, the component of the foam concentrate is analyzed, and SiO2The content is 69.3 percent, and the calculated recovery rate is 82.9 percent;
(h) and dehydrating the flotation underflow to obtain the ferromanganese concentrate.
The ferromanganese concentrate containing 20.7% of Mn and 7.0% of TFe is analyzed, and the calculated metal recovery rates are Mn 90.1% and TFe 90.2%. The ferromanganese concentrate grade is obviously reduced compared with example 2(Mn 26.6%, TFe 9.1%).
Claims (8)
1. A manganese ore enrichment method combining selection and metallurgy comprises the following steps:
(1) mixing and grinding water and manganese ore to prepare manganese ore pulp;
(2) mixing the manganese ore pulp with a leaching agent, controlling the pH value of the manganese ore pulp to be 3-5.5, leaching, and separating to obtain manganese middlings and a leaching solution;
(3) performing reverse flotation desilicification on the manganese middling to obtain flotation froth concentrate as silicon concentrate, and underflow tailings as ferromanganese concentrate;
(4) adding regenerants of quicklime and sulfuric acid into the leachate in sequence to obtain a regenerated leaching agent, returning the regenerated leaching agent to the step (2) for use, and selling magnesium hydroxide and calcium sulfate for sale; ca in regenerated leaching agent2+Concentration not less than 0.5g/L, Mg2+The concentration is not less than 0.2 g/L.
2. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: the manganese ore is pyrolusite, psilomelane, hausmannite, rhodochrosite, calciumusite, manganese calcite or manganese siderite.
3. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: in the step (1), the liquid-solid weight ratio of the water to the manganese ore is 2-6: 1.
4. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: in the step (1), manganese ore and water are ground and mixed to prepare manganese ore pulp, wherein the granularity is equal to or larger than 70% with the granularity of-74 microns.
5. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: in the step (2), the pH value is 4.5-5.5.
6. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: in the step (2), the leaching agent is 1-10 wt% of hydrochloric acid.
7. The beneficiation-metallurgy combined manganese ore enrichment method according to claim 1, wherein: in the step (3), the reverse flotation conditions are as follows: the liquid-solid weight ratio of water to the manganese middlings is 3-8: 1, the pH value is 7-11, the flotation reagent is one or a combination of C12-C18 alkyl primary amine salts, and the dosage is 20-500 g/ton.
8. A combined beneficiation and metallurgy manganese ore enrichment method according to any of the claims 1-7, characterized in that: after treatment, the total recovery rate of manganese is 90-95%, and the mass content of manganese in the ferromanganese concentrate is 25-35%.
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