KR20170076240A - Apparatus for recovering of precious metal and byproducts from ore - Google Patents

Abstract

The present invention is characterized in that the ore is mixed with the ammonium salt pyrolysis agent and pyrolyzed to obtain pyrolytic ore, ammonia and pyrolysis agent-containing flue gas by-products, and the ammonia and acid component contained in the flue gas by-product are collected in an acid and recovered as an ammonium salt solution An ore processing device for crystallizing and reusing it as a thermal decomposition agent; A ferrous metal recovery apparatus for separating a pyrolyzing ore into a leached filtrate and an insoluble residue by water leaching, adjusting the pH and solid-liquid separation, and extracting the leached filtrate by wet extraction to obtain a valuable metal component and an Fe-containing recovered filtrate; And the iron component in the Fe-containing recovered filtrate is concentrated and crystallized into iron salt crystals, and the iron salt crystals are recovered in the form of iron ores after pyrolysis, and the acid gas in the exhaust gas obtained in the recovery of iron ores is recovered as an acid, And recovering valuable metals and byproducts from the ore including the by-product recovery device. The apparatus and method according to the present invention can recover not only valuable metals from ores but also recover and reuse iron components and pyrolysis agents in by-products, thereby improving the economical efficiency and process efficiency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for recovering valuable metals and byproducts from ores,

The present invention relates to an apparatus and a method for recovering valuable metals and byproducts from ores.

In order to recover valuable metals from minerals such as manganese nodules and nickel ores in the future, many efforts are being made to combine mining, beneficiation, and smelting.

The average content of the valuable metals contained in the manganese nodule was 25.4 wt% Mn, 9.5 wt% Fe, 1.28 wt% Ni, 1.02 wt% Cu, 0.24 wt% Co, 0.085 wt% Y, 0.021 wt% %, Nd 0.026% by weight. Manganese nodule, nickel ore, The separation and smelting of crude metals (Mn, Fe, Ni, Co, Cu, etc.) during the process of recovering valuable metals from ores such as smelting byproducts (slag, residue, etc.) account for more than 60% Which accounts for more than 70% of the total.

Conventionally, manganese nodules collected on the ship in the past have to be transported all over the land and transported to a factory which is a smelting facility. Therefore, the transportation cost is estimated to be enormous, and the manganese nodule is crushed as it is, When entering the process, large amounts of reagents such as sulfuric acid, hydrochloric acid, and ammonia are consumed in large amounts. In addition, there is a problem that the environment is adversely affected due to various difficult problems such as securing a landfill for treating residues (waste) after recovery of valuable metals, and the production cost of valuable metals recovered from manganese nodules is high .

The present invention relates to an apparatus and a method for recovering valuable metals and byproducts from ores, and more particularly, to recover not only valuable metals from ores but also recover and reuse iron and pyrolysis products from the by-products to thereby recover valuable metals and by- And to provide a device and method capable of recovering the same.

According to one aspect of the present invention, ore is mixed with an acidic ammonium salt pyrolysis agent and pyrolyzed to obtain a pyrolytic ore, ammonia and a by-product of an acid component of the pyrolysis agent, and the ammonia and an acid component contained in the flue gas by- An ore treatment device for recovering the ammonium salt solution, crystallizing it and reusing it as a thermal decomposition agent;

A ferrous metal recovery apparatus for separating a pyrolyzing ore into a leached filtrate and an insoluble residue by water leaching, adjusting the pH and solid-liquid separation, and extracting the leached filtrate by wet extraction to obtain a valuable metal component and an Fe-containing recovered filtrate; And

The iron component in the Fe-containing recovered filtrate is concentrated and crystallized to be iron salt crystals. The iron salt crystals are recovered in the form of iron ores through pyrolysis, and the acid gas in the exhaust gas obtained in the recovery of iron ores is recovered as an acid, And recovering the by-product from the ore containing the by-product collecting device.

The ore pretreatment device may further include an ore pretreatment device for obtaining a crushed dry burned raw material which is crushed, dried and fired at the front end of the ore treatment device.

The ore pretreatment apparatus includes a particle size adjusting device for obtaining the ore that has been crushed by crushing the ore; And

And a drying and firing apparatus for drying and firing the pulverized ore to obtain pulverized dried bovine light.

The ore processing apparatus includes a mixing device for mixing the crushed dry firing light and the thermal decomposition agent;

An ore pyrolysis apparatus which pyrolytic ores and flue gases are obtained by pyrolysis of pulverized dry pyrolysis mixed with pyrolysis agent;

A dust collecting device for collecting scattered dust in the exhaust gas;

A scrubber for trapping an acid component of a thermal decomposition agent in an acid;

An evaporation concentrator for evaporating and concentrating the collecting solution in which the acid component of the pyrolysis agent in the flue gas is captured; And

And a crystallization drying apparatus in which the evaporated concentrated solution is crystallized and dried, and the pyrolytic component in the concentrated solution is recovered as crystals.

The lean metal recovery apparatus includes a leaching reaction tank for leaching pyrolyzed ore;

A solid-liquid separator for separating the reactants of the leaching reaction tank into a leaching filtrate and an insoluble leaching sludge;

A valuable metal recovering device in which a valuable metal is formed from a leachate containing sludge by wet extraction from the leached filtrate; And

And a solid-liquid separator for separating the valuable metal-containing recovered sludge into solid-liquid separation and recovery into an Fe-containing recovered filtrate and recovered sludge.

The by-

An evaporation concentrator for concentrating the Fe-containing recovered filtrate by evaporation;

A gas-liquid separator for separating the steam used in the evaporation concentrator into a liquid phase and a low-temperature steam;

A steam reuse device for raising the temperature of the low temperature steam and reusing it as an evaporation source;

A steam supply device for supplying steam to the evaporation concentrator;

A heat exchanger for concentrating the Fe-containing recovery filtrate;

A crystallization apparatus in which an iron component in a concentrate of an Fe-containing recovery filtrate is crystallized into iron salt crystals;

A solid-liquid separator for separating the iron salt crystals and the filtrate;

A pyrolysis pyrolysis apparatus which pyrolyzes iron salt crystals;

A cyclone and a dust collector in which scattered iron ore is collected;

An absorption tower in which an acid gas in an exhaust gas discharged from an iron salt decomposition apparatus is recovered as an acid; And

And may include a scrubber where flue-gas is cleaned.

The pyrolyzer may be ammonium sulfate or ammonium chloride.

According to another aspect of the present invention,

Mixing the ore with an ammonium salt pyrolyzer and pyrolyzing to obtain pyrolytic ore and flue gas byproduct;

Collecting the acid component of the pyrolysis agent contained in the obtained by-product of the exhaust gas in the acid, recovering it as an ammonium salt solution, crystallizing and reusing it as a thermal decomposition agent;

Separating the pyrolytic ore into a leached filtrate and an insoluble residue by water leaching, pH adjustment and solid-liquid separation;

Extracting the leached filtrate by wet extraction to obtain a refined metal component and an Fe-containing recovered filtrate;

Concentrating and crystallizing the Fe-containing recovered filtrate to obtain iron salt crystals, pyrolyzing the iron salt crystals and recovering them in the form of iron ores; And

And recovering the pyrolyzate by converting the acid gas in the flue gas generated during pyrolysis of the iron salt crystals to an acid and reusing the recovered pyrolyzate.

The method for recovering valuable metals and by-products according to the present invention may further comprise an ore pretreatment step of crushing, drying and calcining the ore to obtain the crushed dry calcite.

The pyrolysis can be carried out at a temperature of 350 ° C to 550 ° C.

The pyrolysis can be performed for 30 minutes to 90 minutes.

The ore to be pyrolyzed preferably has an average particle size of 5 mm or less.

The pyrolysis can be performed using a pyrolysis agent and ore in a weight ratio of 2: 1 to 4: 1.

The ammonium salt solution may be concentrated by evaporation, crystallization and drying at 0.1 atm, 40 ° C to 1 atm, and 100 ° C.

The water leaching can be carried out at a temperature of 50 ° C to 100 ° C.

The water leaching can be carried out for a period of 5 minutes to 120 minutes.

The water leaching can be performed using water and ore in a weight ratio of 50: 1 to 200: 1.

The pH of the leached filtrate can be adjusted to 2 to 4.

When the pH of the leached filtrate is subjected to wet extraction, the pH of the leached filtrate may be changed from pH 3 to pH 10 to form a valuable metal-containing sludge.

The concentrated crystallization of the Fe-containing recovered filtrate can be carried out at 0.1 atm, 40 ° C to 1 atm, and 100 ° C.

As the thermal decomposition agent, ammonium sulfate or ammonium chloride may be used.

The present invention can recover not only valuable metals from ores but also iron compounds and pyrolysis products from by-products by reusing the valuable metals and by-products from the ores by means of the recovering method and recovering valuable metals. Can be improved. Further, the acid used for collecting the pyrolysis agent can be recovered and reused.

1 schematically shows an apparatus for recovering valuable metals and by-products from ores according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention relates to an apparatus for recovering valuable metals and byproducts from ores, and more particularly, to an apparatus for recovering valuable metals and byproducts from ores including ore processing apparatuses, valuable metal recovering apparatuses, and byproduct recovering apparatuses.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an apparatus for recovering valuable metals and by-products from ores according to the present invention, which will be described in detail with reference to the drawings.

The ore is crushed, dried and calcined in the ore pretreatment apparatus which can optionally be included in the valuable metal and by-product recovery apparatus of the present invention, whereby the crushed dry calcined phosphor can be obtained. The ore pretreatment apparatus may include a particle size regulating apparatus 1 and a drying and calcining apparatus 2. The ore is not particularly limited, but may be, for example, manganese nodule, nickel ore, smelting by-products (slag, residue, etc.).

The ore in the particle size control device 1 is not particularly limited, but is preferably crushed to an average particle size of 5 mm or less. In view of the efficiency of pyrolysis reaction, it is preferable to be crushed to 5 mm or less. Ore crushed to a size of 5 mm or less can be transferred to the drying and firing unit 2. The ore crushed in the drying and firing apparatus (2) is dried and fired to obtain crushed dry fired light. In view of the efficiency of the pyrolysis reaction, the smaller the ore is, the more preferable it is not to limit the particle size of the lower limit.

In the ore processing apparatus, the ore is mixed with the ammonium salt pyrolysis agent and pyrolyzed to obtain pyrolytic ore and flue gas by-product. From the pyrolysis by-product ammonia and the pyrolysis agent-containing flue gas, the acid component of ammonia and pyrolysis agent is collected in the acid, Recovered as a solution, crystallized and reused as a thermal decomposition agent. The ore processing apparatus may include a mixing apparatus 3, an ore pyrolysis apparatus 5, a dust collector 6, a scrubber 7, an evaporation concentrator 9, and a crystallization drying apparatus 10.

The ore may be a crushed dry calcination light obtained in the drying and firing apparatus (2). The crushed dry fired light may be transferred to the mixing apparatus 3 and mixed with the thermal decomposition agent in the mixing apparatus 3. The pyrolysis agent may be introduced into the mixing apparatus 3 from the pyrolyzer storage tank 4. The pyrolysis agent may be, but is not limited to, ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) or ammonium chloride (NH ₄ Cl), for example.

The crushed dry burning light and the pyrolyzing agent may be mixed in a weight ratio of 2: 1 to 4: 1 of a thermal decomposing agent: ore. When the content of the thermal decomposition agent is less than the lower limit, the thermal decomposition reaction does not sufficiently take place, and if it exceeds the upper limit, it is not preferable from the economical viewpoint.

The pulverized dry burned light mixed with the pyrolysis agent is transferred to the ore pyrolysis apparatus 5, and the pyrolysis ore and pyrolysis by-product can be obtained by pyrolyzing the dried pyrolysis light broken in the ore pyrolysis apparatus 5. The exhaust gas is a very high temperature gas, and not only ammonia but also acid groups (SO ₄ ^{2 -} , Cl ^-, etc.) of the thermal decomposition agent may exist in various forms. In the ore pyrolysis unit (5), various metal components contained in the ore are pyrolyzed as follows. The following pyrolysis reaction is a case where ammonium pyrosulfate is used as a thermal decomposition agent.

[Pyrolysis reaction formula]

Fe ₂ O ₃ + 2 (NH ₄ ) ₂ SO ₄ + O ₂ = 2FeSO ₄ + 2NH ₃ + 5H ₂ O + N ₂

_{MnO 2 + (NH 4) 2} SO 4 = MnSO 4 + 2NH 3 + H 2 O + 1 / 2O 2

_{NiO + (NH 4) 2 SO} 4 = NiSO 4 + 2NH 3 + H 2 O

_{CuO + 2 (NH 4) 2} SO 4 = CuSO 4 + 2NH 3 + H 2 O

_{CoO + 2 (NH 4) 2} SO 4 = CoSO 4 + 2NH 3 + H 2 O

The pyrolysis can be carried out at a temperature of 350 ° C to 550 ° C. If the pyrolysis temperature is less than 350 ° C, the pyrolysis reaction does not sufficiently take place. If the pyrolysis temperature is more than 550 ° C, the pyrolysis conversion rate is lowered due to the secondary pyrolysis reaction of the pyrolysis product.

The pyrolysis can be performed for a time of 30 minutes to 90 minutes. When the pyrolysis time is less than 30 minutes, the pyrolysis reaction does not sufficiently take place, which is undesirable. When the pyrolysis time exceeds 90 minutes, it is not preferable from the economical point of view.

It is preferable that the pyrolysis is performed on an ore having an ore particle size of 5 mm or less. When the ore particle size exceeds 5 mm, pyrolysis reaction does not sufficiently take place, which is not preferable. The smaller the ore size in the pyrolysis reaction efficiency is, the more preferable the lower limit of the ore particle size is not particularly limited.

The pyrolytic ore is stored in the pyrolysis ore storage tank 12 and then transferred to the leaching reaction tank 13 to be leached.

On the other hand, the scattered dust in the exhaust gas obtained as a by-product of the pyrolysis reaction in the pyrolysis apparatus 5 is collected in the dust collecting apparatus 6 and the ammonia and the acid component (SO ₄ ^{2 -} or Cl ^- ) of the pyrolysis agent are collected in a scrubber 7, collected as an ammonium salt solution and transferred to the flue gas collecting solution reservoir 8. The acid may be sulfuric acid, hydrochloric acid, and the like. The ammonium salt solution may be an ammonium sulfate salt solution or an ammonium chloride salt solution.

The acidic ammonium salt solution of the flue gas collecting solution reservoir 8 is concentrated by evaporation in the evaporator 9 and crystallized and dried in the crystallization drying apparatus 10 and recovered in the form of ammonium crystals (ammonium sulfate or ammonium chloride).

The ammonium salt solution may be concentrated by evaporation, crystallization and drying at 0.1 atm, 40 ° C to 1 atm, and 100 ° C. The pressure and temperature ranges are preferable in terms of energy efficiency and crystal recovery efficiency.

The ammonium salt crystals may be transferred to the recovered pyrolysis storage tank 11 and stored therein. The ammonium salt crystals are then reused as a thermal decomposition agent such as ore, for example, manganese nodule, nickel ore, and smelting by-products (slag, residue, etc.). That is, the recovered ammonium salt crystals may be transferred from the recovered thermal decomposition agent reservoir 11 to the thermal decomposition agent reservoir 4 and introduced into the mixing apparatus 3 in the thermal decomposition agent reservoir 4. On the other hand, the dust recovered in the dust collecting device 6 is transferred to the mixing device 3.

In the crude metal recovery apparatus, the leached filtrate obtained by leaching pyrolytic ore and adjusting the pH of the leaching reaction and solid-liquid separation can be used to obtain sludge containing valuable metal components and recovered Fe-containing filtrate. The valuable metal recovering apparatus includes a leaching reaction tank 13, a solid-liquid separating apparatus 15, a valuable metal recovering apparatus 18, and a solid-liquid separating apparatus 19.

The pyrolytic ore in the pyrolysis ore storage tank 12 is transferred to the leaching reaction tank 13, and the pyrolysis ore is leached into water in the leaching tank 13 (water leaching). Water is introduced into the leaching reaction tank (13) from the water storage tank (14). The water-leaching reaction of the pyrolytic ore causes leaching of the valuable metal of the pyrolytic ore. Examples of the valuable metal include, but are not limited to, Mn, Fe, Ni, Co, Cu, and the like.

The water leaching can be carried out at a temperature of 50 ° C to 100 ° C. If the water leaching temperature is less than 50 캜, the leaching reaction does not sufficiently take place, which is undesirable. If it exceeds 100 캜, it is not preferable from the economical point of view. The water leaching can be carried out for a time of 5 minutes to 120 minutes. If the water leaching time is less than 5 minutes, the leaching reaction does not sufficiently take place, which is undesirable. If it exceeds 120 minutes, it is not preferable from the economical viewpoint.

The water leaching can be performed at a weight ratio of water: ore of 50: 1 to 200: 1. If the content of water is less than the lower limit value, the leaching reaction does not sufficiently occur, and if the content of water exceeds the upper limit value, it is not preferable from the economical point of view.

In the leaching reaction tank 13, the leaching reaction may be adjusted to a pH of 2 to 4 in order to remove colloidal impurities in the leaching reaction before the solid-liquid separation. If the pH is less than 2, impurities are not sufficiently removed, and if the pH exceeds 4, it is not preferable from the economical point of view. The pH may be adjusted using ammonia or the like, but is not limited thereto. After the pH of the leaching reactant is adjusted as described above, the pH-regulated leaching reaction is separated into the leaching filtrate and the insoluble leaching sludge in the solid-liquid separator 15. The leached filtrate is transferred to the leached filtrate reservoir (17), and the insoluble leached sludge is transferred to the leached sludge reservoir (16). The insoluble leachate sludge can be discarded or recycled as aggregate for civil engineering, rare metals recovery ore.

The leached filtrate of the leached filtrate reservoir 17 is transferred to the lean metal recovery apparatus 18 where the lean metal is recovered by the wet extraction method to obtain the Fe-containing recovered filtrate. In the wet extraction method, a valuable metal is recovered by a cementation method, or an ion exchange method, a solvent extraction method or the like is applied to separate each valuable metal, and then the valuable metal component is recovered in the form of hydroxide sludge by an alkali neutralization reaction.

In the alkali neutralization reaction, the pH is adjusted to 3 to 10. By adjusting the pH to the above range, the valuable metal component forms a hydroxide sludge. In the alkali neutralization reaction, the pH can be adjusted by using ammonia or the like, but is not limited thereto.

As described above, the valuable metal is converted into the hydroxide sludge in the valuable metal recovering device 18 and transferred to the solid-liquid separator 19. The Fe-containing recovered filtrate separated by the Fe-containing recovered filtrate (hereinafter referred to as "recovered filtrate") and the recovered sludge in the solid-liquid separator 19 is transferred to the recovered-filtrate storage tank 21, and the recovered sludge is recovered in the recovered sludge storage tank 20 . The recovered sludge can be used as an industrial base material.

In the by-product recovery apparatus, the iron component is concentrated and crystallized and pyrolyzed from the Fe-containing recovered filtrate and recovered in the form of iron ore. The acid gas in the exhaust gas generated in the recovery of iron ore is converted to an acid and reused for recovery of the pyrolysis agent. The byproduct collecting device includes an evaporation concentrator 22, a gas-liquid separator 23, a steam recycling device 24, a steam supply device 25, a heat exchanger 26, a crystallization device 27, A pyrolysis pyrolysis unit 30, a cyclone 31, a dust collector 31 ', an absorption tower 33, and a scrubber 34.

The recovered filtrate of the recovered filtrate storage tank (21) is transferred to the evaporation concentrator (22) and evaporated and concentrated. At this time, steam supplied from the steam supply device 25 to the evaporation and concentration device 22 is used as a heat source for evaporation and concentration. After being used in the evaporation concentrator 22, the discharged steam is transferred to the gas-liquid separator 23 to be separated into a liquid phase and a gaseous phase (low-temperature steam (steam having a lower temperature than steam used as a heat source)). The liquid phase is discharged and the low temperature steam separated by the gas-liquid separator 23 is reused in the evaporation concentrator 22 via the steam recycling device 24 and the steam supply device 25. [ In the steam recycling apparatus 24, the low-temperature steam is mechanically compressed or the temperature of the low-temperature steam is increased by using the heat of the new steam to be reused as an evaporation source.

On the other hand, the concentrated liquid of the recovered filtrate concentrated by evaporation in the evaporation concentrator 22 is transferred to the crystallizer 27 via the heat exchanger 26, the iron component contained in the recovered filtrate is crystallized into the iron salt, 28) and separated into filtrate and iron salt crystals. In the heat exchanger (26), the evaporation and concentration of the concentrate further proceeds.

The above-mentioned evaporation concentration and crystallization and drying can be carried out under the conditions of 0.1 atm, 40 ° C to 1 atm, and 100 ° C. Concentration and crystallization by evaporation in the pressure and temperature range is preferable in view of the iron salt crystal recovery efficiency and energy efficiency.

The filtrate discharged from the solid-liquid separator 28 is transferred to the crystallization device 27, and the iron salt crystals are transferred to the iron salt crystal reservoir 29. The iron salt crystals of the iron salt crystal storage tank 29 are transferred to the iron salt pyrolysis apparatus 30, pyrolyzed and separated into iron ore and exhaust gas. The iron salt crystals are pyrolyzed as in the following iron salt pyrolysis reaction formula.

[Iron salt pyrolysis reaction formula]

2FeSO ₄ + H ₂ O + O ₂ = Fe ₂ O ₃ + H ₂ SO ₄

2FeCl ₂ + 2H ₂ O + ½O ₂ = Fe ₂ O ₃ + 4HCl

The iron ores obtained by pyrolysis in the iron salt pyrolysis apparatus 30 are in the form of particles in which iron ore powders are aggregated with each other. This particulate iron ore is discharged from the rear end of the iron salt pyrolysis apparatus 30 to the recovered iron ore storage tank 32. Among the iron ores obtained by pyrolysis in the iron salt pyrolysis apparatus 30, the arsenic iron ores are collected in the cyclone 31 and the dust collector 31 'and discharged to the recovered iron ore storage tank 32.

The exhaust gas discharged from the iron salt decomposition apparatus 30 is sent to the absorption tower 33 via the cyclone 31 and the dust collector 31 'and condensed. On the other hand, the exhaust gas contains an acid component, for example, SO ₄ ^{2 -} or Cl ^- as an acid gas component in the ammonium salt used as the thermal decomposition agent of the ore. In the upper layer of the absorption tower 33, water is supplied to absorb the acid gas component in the flue gas, and these acid gases are absorbed in water and recovered as an acid. The acid gas may be sulfuric acid gas, hydrochloric acid gas, or the like.

In the lower part of the absorption tower 33, the recovered acid is transferred to the rotary water storage tank 38 by the pump 37. The acid recovered in the rotating-water storage tank 38 may be supplied to the scrubber 7. [ The acid may be sulfuric acid or hydrochloric acid. On the other hand, the flue gas that has passed through the top of the absorption tower 33 is sent to the scrubber 34 to clean the acid gas contained in the flue gas with an alkaline substance or the like. The alkaline material may be, but is not limited to, NaOH, for example. The gas passed and discharged on the scrubber 34 is sent to the stack 35 and discharged into the atmosphere. The solution discharged after being cleaned in the lower part of the scrubber 34 is sent to the wastewater treatment tank 36.

The valuable metal and byproduct recovery apparatus of the present invention can recover the entire amount of the pyrolysis agent and reuse it. Further, the iron component in the filtrate is recovered in iron ore form. Therefore, valuable metals and by-products can be recovered from the ore at low cost, and the efficiency of the process can be improved. Further, the acid used for collecting the pyrolysis agent can be recovered and reused.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the method for recovering valuable metals and byproducts. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

(Example 1)

The ore used in the ore pyrolysis reaction was found to have an average content of 25% Mn, 9.5% Fe, 1.28% Ni, 1.02% Cu, and 0.24% Co based on weight. The reaction temperature was changed to 300 ° C., 350 ° C., 450 ° C., 550 ° C. and 600 ° C. under the conditions of the ore particle size of 0.1 mm or less, the reaction time of 60 minutes and the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) The ore was pyrolyzed. The decomposition rate of the crude metal according to the reaction temperature is shown in Table 1, by leaching the pyrolysis reaction product in each condition and quantitatively analyzing the metal component in the leaching solution. At this time, the leaching conditions were a temperature of 100 ° C, a time of 120 minutes, and a weight ratio of water / ore to 200.

In the table below,

(%) = (Amount of metal component in the leaching solution / amount of metal component in the ore) x 100,

The leach rate (%) of the valuable metal = (the amount of the metal component in the leached liquid / the amount of the metal component in the pyrolyzing ore) x 100.

division Pyrolysis reaction temperature (캜) 300 350 450 550 600 Valuable metal
Decomposition rate (%) 75 95 95 95 72

As can be seen from Table 1, the pyrolysis reaction temperature of the ore was found to be suitably in the range of 350 ° C to 550 ° C.

(Example 2)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The reaction time was changed to 5 minutes, 30 minutes, 60 minutes, and 90 minutes under the condition of the ore particle size of 0.1 mm or less, the reaction temperature of 350 ° C, the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) . The pyrolysis reaction products in each condition were leached out with water, and the crude metal components in the leaching solution were quantitatively analyzed. The decomposition conversion rates of the valuable metals according to the reaction time are shown in Table 2 below. At this time, the leaching conditions were a temperature of 100 ° C, a time of 120 minutes, and a weight ratio of water / ore to 200.

division Pyrolysis reaction time (min) 5 30 60 90 Valuable metal
Decomposition rate (%) 65 80 95 90

As can be seen from Table 2, the pyrolysis reaction time of the ore was 30 to 90 minutes.

(Example 3)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The ores were pyrolyzed by changing the ore particle size to 0.1 mm, 0.2 mm, 3 mm, 5 mm, and 7 mm under the conditions of a reaction temperature of 350 ° C., a reaction time of 60 minutes, and a pyrolyzer ((NH ₄ ) ₂ SO ₄ ) . Table 3 shows the decomposition rate of the crude metal according to the ore particle size by leaching the pyrolysis reaction product in each condition and quantitatively analyzing the metal component in the leach solution. At this time, the leaching conditions were a temperature of 100 ° C, a time of 120 minutes, and a weight ratio of water / ore to 200.

division Pyrolysis ore particle size (mm) 0.1 0.2 3 5 7 Conversion of crude oil to metal (%) 95 75 60 50 30

As shown in Table 3, the particle size of the pyrolysis ore of the ore was found to be less than 5 mm.

(Example 4)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The ore was pyrolyzed by changing the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore to 1, 2 and 4 under the conditions of ore particle size of 0.1 mm or less, reaction temperature of 350 ° C. and reaction time of 60 minutes. The decomposition conversion rates of the valuable metals according to the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore are shown in Table 4 below by leaching the pyrolysis reaction product in each condition and quantitatively analyzing the metal component in the leaching solution . At this time, the leaching conditions were a temperature of 100 ° C, a time of 120 minutes, and a weight ratio of water / ore to 200.

division Weight ratio of pyrolyzer / ore One 2 4 Valuable metal
Decomposition rate (%) 68 90 95

As can be seen from Table 4, the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore of the ore was suitably from 2 to 4.

(Example 5)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The reaction products produced by the pyrolysis reaction were subjected to leaching with water at a weight ratio of water / reaction product (pyrolytic ore) of 200 and leaching time of 120 minutes at 25 ° C, 50 ° C, 75 ° C and 100 ° C ). Table 5 shows the leaching rates of the valuable metals according to the water leaching reaction temperature by quantitatively analyzing the metal components in the leach solution under the respective conditions. At this time, the pyrolysis condition was the ore particle size of 0.1 mm or less, the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore was 4, the reaction temperature was 350 ° C., and the reaction time was 60 minutes.

division Water leaching reaction temperature (캜) 25 50 75 100 Percentage of Lean Metal Leach (%) 68 85 85 90

As can be seen from Table 5, the water leaching temperature of the pyrolytic ore was found to be suitably from 50 to 100 ° C.

(Example 6)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The reaction product produced by the pyrolysis reaction was subjected to leaching reaction at a weight ratio of water / reaction product (pyrolysis ore) of 200 and leaching temperature of 100 ° C for 5 minutes, 30 minutes, 60 minutes and 120 minutes, ). Table 6 shows the leaching rates of the valuable metals according to the water leaching reaction time by quantitatively analyzing the metal components in the leach solution under the respective conditions. At this time, the pyrolysis condition was the ore particle size of 0.1 mm or less, the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore was 4, the reaction temperature was 350 ° C., and the reaction time was 60 minutes.

division Water leaching reaction time (min) 5 30 60 120 Percentage of Lean Metal Leach (%) 80 80 80 90

As can be seen in Table 6, the reaction time of the water decomposition ore of the pyrolytic ore was suitably from 5 to 120 minutes.

(Example 7)

The ores used in the pyrolysis of ore were 25.4% of Mn, 9.5% of Fe, 1.28% of Ni, 1.02% of Cu and 0.24% of Co. The reaction products formed by pyrolysis reaction were subjected to leaching (water leaching) by changing the weight ratio of water / reaction product (pyrolytic ore) to 50, 100, 150 and 200 at a leaching reaction temperature of 100 ° C and a leaching reaction time of 120 minutes . The leach rates of the precious metals according to the ratio of water / reaction products by quantitative analysis of the precious metal components in the leachate under the respective conditions are shown in Table 7 below. At this time, the pyrolysis condition was the ore particle size of 0.1 mm or less, the weight ratio of the thermal decomposition agent ((NH ₄ ) ₂ SO ₄ ) / ore was 4, the reaction temperature was 350 ° C., and the reaction time was 60 minutes.

division Water / reaction product ratio 50 100 150 200 Percentage of Lean Metal Leach (%) 70 80 80 90

As can be seen in Table 7 above, the weight ratio of the water immersion release / reaction product was found to be suitably from 50 to 200.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It will be obvious to those of ordinary skill in the art.

1: Particle size regulating device 2: Drying and firing device
3: Mixing device 4: Pyrolysis agent storage tank
5: Ore Pyrolysis Unit 6: Dust Collector
7: Scrubber 8: Flue gas by-product collection solution reservoir
9: Evaporation concentrator 10: Crystallization dryer
11: recovered pyrolysis agent storage tank 12: pyrolysis ore storage tank
13: leaching reaction tank 14: water storage tank
15: Solid-liquid separator 16: Leachate sludge storage tank
17: Leaching filtrate storage tank 18: Oil-rich metal recovery device
19: Solid-liquid separator 20: Recovery sludge storage tank
21: recovery filtrate storage tank 22: evaporation concentrator
23: gas-liquid separator 24: steam recycling device
25: steam supply device 26: heat exchanger
27: crystallization device 28: solid-liquid separation device
29: Iron salt crystal storage tank 30: Iron salt pyrolysis apparatus
31: Cyclone, 31 ': Dust collector
32: recovered iron ore storage tank 33: absorption tower
34: Scrubber 35: Stack
36: wastewater treatment tank 37: pump
38: Fish storage tank

Claims (21)

The ore is mixed with the ammonium salt pyrolysis agent and pyrolyzed to obtain the pyrolysis ore and the by-product by-product containing the acid component of the ammonia and the pyrolysis agent. The ammonia and the acid component contained in the flue gas by-product are collected in the acid, recovered as the ammonium salt solution, Ore processing equipment for zero reuse;
A crude metal recovering apparatus for recovering a valuable metal component and an Fe-containing recovered filtrate by separating the pyrolytic ore into water leached, adjusting the pH and solid-liquid separation, separating the leached filtrate and the insoluble residue, and extracting the leached filtrate by wet extraction; And
The iron component in the Fe-containing recovered filtrate is concentrated and crystallized to become iron salt crystals. The iron salt crystals are recovered in the form of iron ores after pyrolysis, and the acid gas in the exhaust gas obtained in the recovery of iron ores is recovered as an acid and reused in the recovery of the pyrolysis agent And recovering valuable metals and byproducts from ores containing byproduct recovery devices.
The method according to claim 1,
Further comprising an ore pretreatment device for obtaining a crushed dry calcite which is crushed, dried and calcined at the front end of the ore processing apparatus.
3. The ore pretreatment apparatus according to claim 2,
A particle size adjusting device for crushing the ore to obtain a crushed ore; And
And a drying and calcining apparatus for drying and calcining the crushed ore to obtain a crushed dry calcite, and recovering the valuable metal and by-product from the ore.
2. The ore processing apparatus according to claim 1,
Mixing apparatus for mixing ore and pyrolyzer;
An ore pyrolysis apparatus which pyrolytic ores and flue gases are obtained by pyrolysis of pulverized dry pyrolysis mixed with pyrolysis agent;
A dust collecting device for collecting fugitive dust in the flue gas;
A scrubber for trapping an acid component of a pyrolysis agent in an exhaust gas into an acid;
An evaporation concentrator for evaporating and concentrating the collecting solution in which the acid component of the pyrolysis agent in the flue gas is captured; And
The crystallization drying apparatus in which the evaporated and concentrated solution is crystallized and dried to recover the components of the thermal decomposition agent into crystals
Valuable metals and byproduct recovery devices from ores containing.
The method according to claim 1, wherein the valuable metal recovering device
A leaching tank for leaching pyrolyzed ore;
A solid-liquid separator for separating the reactants of the leaching reaction tank into a leaching filtrate and an insoluble leaching sludge;
A valuable metal recovering device in which a valuable metal is formed from a leachate containing sludge by wet extraction from the leached filtrate; And
And a solid-liquid separator for separating the recovered valuable metal-containing recovered sludge into solid-liquid separated and recovering the Fe-containing recovered filtrate and recovered sludge.
The apparatus according to claim 1, wherein the by-
An evaporation concentrator for concentrating the Fe-containing recovered filtrate by evaporation;
A gas-liquid separator for separating the liquefied steam used in the evaporation concentrator into a liquid phase and a low-temperature steam;
A steam reuse device for raising the temperature of the low temperature steam and reusing it as an evaporation source;
A steam supply device for supplying steam to the evaporation concentrator;
A heat exchanger for concentrating the Fe-containing recovery filtrate;
A crystallization apparatus in which an iron component in a concentrate of an Fe-containing recovery filtrate is crystallized into iron salt crystals;
A solid-liquid separator for separating the iron salt crystals and the filtrate;
A pyrolysis pyrolysis apparatus which pyrolyzes iron salt crystals;
A cyclone and a dust collector in which scattered iron ore is collected;
An absorption tower in which an acid gas in an exhaust gas discharged from an iron salt decomposition apparatus is recovered as an acid; And
A valuable metal and byproduct recovery device from an ore containing a scrubber where the flue gas is cleaned.
The apparatus of claim 1, wherein the pyrolysis agent is ammonium sulfate or ammonium chloride.
Mixing the ore with an ammonium salt pyrolyzer and pyrolyzing to obtain pyrolytic ore and flue gas byproduct;
Collecting the acid component of the pyrolysis agent contained in the obtained flue gas by-product into an acid, recovering it as an acidic ammonium salt solution, crystallizing and reusing it as a thermal decomposition agent;
Separating the pyrolytic ore into a leached filtrate and an insoluble residue by water leaching, pH adjustment and solid-liquid separation;
Extracting the leached filtrate by wet extraction to obtain a refined metal component and an Fe-containing recovered filtrate;
Concentrating and crystallizing the Fe-containing recovered filtrate to obtain iron salt crystals, pyrolyzing the iron salt crystals and recovering them in the form of iron ores; And
And converting the acid gas in the flue gas generated during pyrolysis of the iron salt crystals to an acid and reusing it for recovery of the pyrolysis agent.
9. The method of claim 8,
A method of recovering valuable metals and byproducts from ores, further comprising an ore pretreatment step of crushing, drying and calcining the ore to obtain said crushed dry calcite.
The method for recovering valuable metals and byproducts according to claim 8, wherein the pyrolysis is performed at a temperature of 350 ° C to 550 ° C.
The method for recovering valuable metals and byproducts according to claim 8, wherein the pyrolysis is carried out for 30 minutes to 90 minutes.
The method for recovering valuable metals and byproducts according to claim 8, wherein the pyrolyzing ore has an average particle size of 5 mm or less.
The method for recovering valuable metals and by-products according to claim 8, wherein the pyrolysis is performed using a pyrolysis agent and ore in a weight ratio of 2: 1 to 4: 1 pyrolyzer: ore.
The method for recovering valuable metals and by-products according to claim 8, wherein the concentration of the acidic ammonium salt solution is carried out by evaporation, crystallization and drying at 0.1 atm, 40 ° C to 1 atm, and 100 ° C.
The method for recovering valuable metals and byproducts according to claim 8, wherein the water leaching is carried out at a temperature of 50 ° C to 100 ° C.
The method for recovering valuable metals and byproducts according to claim 8, wherein the water leaching is performed for 5 to 120 minutes.
The method of claim 8, wherein the water leaching is performed using water and ore in a weight ratio of water: ore of 50: 1 to 200: 1.
The method of claim 8, wherein the pH adjustment is adjusted to a pH of from 2 to 4.
The method for recovering valuable metals and byproducts according to claim 8, wherein the pH of the leached filtrate is adjusted to a pH of from 3 to 10 during wet extraction to form a valuable metal-containing sludge.
The method for recovering valuable metals and byproducts according to claim 8, wherein the concentrated crystallization of the Fe-containing recovered filtrate is carried out at 0.1 atm, 40 ° C to 1 atm, and 100 ° C.
The method of claim 8, wherein the pyrolysis agent is ammonium sulfate or ammonium chloride.

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