CN112458278A - Application and preparation method of cobalt-nickel-iron multi-element alloy concentrate and cobalt-manganese multi-metal oxide ore dressing-smelting combined method for solid-phase metallization reduction - Google Patents

Abstract

The invention provides an application and a preparation method of cobalt-nickel-iron multi-element alloy concentrate and a solid-phase metallization reduction cobalt-manganese multi-metal oxide ore dressing and metallurgy combined method, and relates to the technical field of cobalt-manganese multi-metal oxide ore dressing and metallurgy. The application comprises the application of cobalt-nickel-iron multi-element alloy concentrate as a metal agglomerating agent in cobalt-manganese multi-metal oxide ores; the preparation method comprises the steps of carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomerating agent, and then carrying out magnetic separation to obtain cobalt-nickel-iron multi-element alloy concentrate enriched with cobalt and nickel. The combined dressing and smelting method adopts the nickel-cobalt-iron multi-component alloy concentrate as the metal agglomerating agent to prepare cobalt-nickel-enriched cobalt-nickel-iron multi-component alloy concentrate and manganese-enriched manganese concentrate, and the cobalt-nickel-iron multi-component alloy concentrate is separated and recovered with cobalt and nickel. The invention uses the self-produced cobalt-nickel-iron multi-element alloy concentrate to circularly prepare the ultra-fine metal nucleation agglomeration metal agglomeration agent, and has the advantages of simple process, small post-treatment amount, high recovery rate, low energy consumption and low cost.

Description

Application and preparation method of cobalt-nickel-iron multi-element alloy concentrate and cobalt-manganese multi-metal oxide ore dressing-smelting combined method for solid-phase metallization reduction

Technical Field

The invention relates to the technical field of cobalt-manganese multi-metal oxide ore dressing and metallurgy, in particular to an application and a preparation method of cobalt-nickel-iron multi-element alloy concentrate and a cobalt-manganese multi-metal oxide ore dressing and metallurgy combined method for solid-phase metallization reduction.

Background

The cobalt-manganese multi-metal oxide ore generally refers to multi-metal complex oxide ore rich in multiple valuable elements such as cobalt, nickel, copper, manganese, iron and the like, and is divided into seabed multi-metal nodule, seabed cobalt-rich crust, land multi-metal manganese oxide ore and the like. The ore is characterized by associated multiple metals, low grade, and containing a large amount of elements such as iron, manganese and the like besides nickel, cobalt and copper. Because the mineral has complex mineral embedding characteristics, direct mineral separation is difficult to separate and enrich nickel, cobalt and copper, and the direct mineral separation is generally directly processed by a metallurgical process, and the main method comprises the following steps: high-temperature high-pressure leaching method, normal-pressure leaching method with addition of reducing agent, reduction roasting-leaching method, smelting method and other processes. However, the direct smelting needs a large amount of reducing agents and smelting aids, so that the cost is high, the treatment capacity is large, and the economy is poor.

Direct high-temperature reduction smelting is adopted, or reduction roasting is firstly carried out, then electric furnace melting is carried out, although the alloy containing nickel, cobalt and copper and the slag containing manganese are easily obtained, the alloy and the slag after discharging and cooling are hard, the subsequent crushing and ore grinding difficulty is high, the cost is high, the subsequent wet recovery is not facilitated, and the high-temperature melting reduction is adopted, so that the energy consumption is high. Actually, from the analysis of reaction thermodynamics, nickel, cobalt, copper, iron and the like in the cobalt-manganese multi-metal oxide ore are easily reduced into metals, namely, the metallization reduction can be realized at a lower temperature, but due to the low reaction temperature, the materials are in a solid state or a semi-molten state, and the reduced metal nickel, cobalt, iron and the like lack nucleation and aggregation conditions, so that the alloy particle size formed by the metals such as cobalt, nickel, iron and the like is very fine and is included in a slag phase, so that the enrichment ratio and recovery rate of cobalt, nickel and the like in the subsequent direct magnetic separation are not high, and tailings produced by the magnetic separation need to be further recovered through flotation scavenging or hydrometallurgical treatment.

In view of this, in the prior art, a sulfur-containing substance and a metal sulfide are added as additives to be mixed into cobalt-manganese polymetallic oxide ores, and the surface properties of alloy particles generated in the process of metallization reduction are improved through the chemical action of high-temperature matte formation and gold capture, so that the alloy can be more easily migrated and aggregated, and particularly, the collection of metal copper is obvious, thereby improving the recovery effect of metallization reduction-magnetic separation. However, the sulfur is introduced into the method, so that the content of sulfur and manganese in the magnetic separation concentrate is increased, the alloy magnetic performance is weakened due to the wrapping effect of the sulfur, and the grade of valuable metals in the magnetic separation concentrate is reduced, so that the subsequent treatment capacity and cost for recovering metals such as nickel, cobalt and the like are increased. Meanwhile, the method also has the problem of environmental protection pressure caused by sulfur-containing flue gas generated in the reduction process.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide an application of cobalt-nickel-iron multi-element alloy concentrate as a metal agglomerating agent in cobalt-manganese multi-metal oxide ore dressing and metallurgy, and the cobalt-nickel-iron multi-element alloy concentrate as the metal agglomerating agent can effectively trap dispersed ultra-fine metal or alloy particles newly generated in the solid-phase metallization reduction process of the cobalt-manganese multi-metal ore, promote the metallization reduction process, accelerate the aggregation and growth of newly generated metal or alloy to facilitate ore dressing and separation, and improve the dressing and metallurgy efficiency.

The second purpose of the invention is to provide a preparation method of the cobalt-nickel-iron multi-element alloy concentrate, which has the advantages of simple process, less post-treatment amount and high recovery rate.

The third purpose of the invention is to provide a cobalt-manganese multi-metal oxide ore dressing and smelting combined method based on solid-phase metallization reduction, which aims to solve the problems of higher cost and poor economy of the existing smelting method during smelting and improve the recovery effect of metallization reduction-magnetic separation.

The purpose of the invention is realized by the following technical scheme:

the invention provides an application of cobalt-nickel-iron multi-element alloy concentrate as a metal agglomeration agent in cobalt-manganese multi-metal oxide ore dressing and smelting.

The invention also provides a preparation method of the cobalt-nickel-iron multicomponent alloy concentrate, which comprises the following steps:

step A, carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomeration agent;

and step B, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate.

Further, in the step a, the metal agglomeration agent comprises at least one of iron powder, cobalt-nickel-iron multi-element alloy concentrate or iron concentrate powder;

preferably, the addition amount of the metal agglomerating agent is 5-30% of the mass of the cobalt-manganese multi-metal oxide ore powder.

Further, in step a, the metallization reduction roasting is reduced by using a reducing agent, wherein the reducing agent comprises a first reducing agent and an optional second reducing agent;

wherein the first reducing agent comprises pulverized coal and/or coke powder;

the second reducing agent comprises at least one of carbon powder, carbon monoxide, hydrogen, coal gas or natural gas;

preferably, the addition amount of the reducing agent is 2-15% of the total mass of the cobalt-manganese multi-metal oxide ore.

Further, in the step A, the mixture also comprises a metallization auxiliary agent;

preferably, the metallization aid comprises at least one of fluoride, sulfide, sulfate, or silica;

preferably, the addition amount of the metallization promoter is not more than 10% of the total mass of the cobalt-manganese multi-metal oxide ore. Preferably, the addition amount of the metallization promoter is not more than 10% of the total mass of the cobalt-manganese multi-metal oxide ore.

Further, in the step A, the temperature of the metallization reduction roasting is 400-1200 ℃;

preferably, the temperature of the metallization reduction roasting is 900-1150 ℃.

Further, in the step a, the cobalt-manganese multi-metal oxide ore fine ore comprises at least one of a seabed multi-metal nodule fine ore, a seabed cobalt-rich crust fine ore or a land multi-metal oxide manganese ore fine ore;

preferably, the cobalt-nickel-iron multi-element alloy concentrate comprises iron, optionally cobalt and optionally nickel.

Further, in the step A, the granularity of the cobalt-manganese multi-metal oxide ore powder is less than 0.25mm;

preferably, the granularity of the cobalt-manganese multi-metal oxide ore powder is less than 0.074mm and accounts for more than 80%;

preferably, in the step B, the magnetic field intensity of the magnetic separation is 100 mT-1000 mT.

The invention also provides a cobalt-manganese multi-metal oxide ore dressing and smelting combined method based on solid-phase metallization reduction, which comprises the following steps:

step a, carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomeration agent;

b, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate and manganese-enriched manganese concentrate;

c, separating and recovering cobalt and nickel from the cobalt-nickel-iron multicomponent alloy concentrate;

the metal agglomeration agent in the step a is the cobalt-nickel-iron multi-element alloy concentrate or the cobalt-nickel-iron multi-element alloy concentrate prepared by the preparation method of the cobalt-nickel-iron multi-element alloy concentrate provided by the invention.

Further, in the step c, slurrying, leaching and purifying and separating the cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate by using a leaching agent to recover cobalt and nickel;

preferably, the leaching agent comprises at least one of a sulfuric acid solution, a hydrochloric acid solution, or an ammoniacal solution.

Compared with the prior art, the invention has the following beneficial effects:

the application of the cobalt-nickel-iron multi-element alloy concentrate as a metal agglomerating agent in cobalt-manganese multi-metal oxide ore dressing and smelting expands the selection of the metal agglomerating agent in the cobalt-manganese multi-metal oxide ore dressing and smelting method, provides a new metal agglomerating agent with high quality and low cost, reduces the temperature in the metallization reduction process and saves energy consumption. Meanwhile, the magnetism of the multi-element alloy concentrate can also capture newly generated and dispersed ultrafine metal or alloy particles, is more favorable for the aggregation and growth of the newly generated metal and alloy particles, is favorable for strengthening the collection of the ultrafine alloy in the magnetic separation process, is easy for magnetic separation and enrichment, and can further reduce the temperature required by solid-phase metallization reduction.

The preparation method of the cobalt-nickel-iron multi-metal alloy concentrate provided by the invention has the advantages that the cobalt-nickel-iron multi-metal alloy is efficiently enriched and recovered from the cobalt-manganese multi-metal oxidized ore containing nickel, cobalt, copper, manganese and iron, the process is simple, the post-treatment capacity is small, the recovery rate is high, the energy consumption is low, the cost is low, and the environmental friendliness is good.

The combined method for selecting and smelting cobalt-manganese multi-metal oxide ores based on solid-phase metallization reduction provided by the invention realizes source separation of cobalt-nickel-iron alloy concentrate and manganese concentrate by adopting a combined process of smelting firstly and then selecting, simplifies subsequent recovery processes and improves the comprehensive utilization rate of resources.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

According to the first aspect of the invention, the invention provides an application of cobalt-nickel-iron multi-element alloy concentrate as a metal agglomerating agent in cobalt-manganese multi-metal oxide ore dressing and metallurgy. The magnetic cobalt-nickel-iron multi-element alloy is used as a newly generated and dispersed metal agglomerating agent of ultra-fine metal or alloy to promote the dissociation, separation and aggregation of nickel, cobalt, iron and the like in the cobalt-manganese multi-metal oxide ore, so that the magnetic separation of the roasted material is easily carried out to obtain manganese concentrate and cobalt-nickel-iron multi-element alloy concentrate, the subsequent smelting treatment amount is reduced, and the purification and impurity removal processes are simplified.

According to a second aspect of the present invention, the present invention provides a method for preparing a cobalt-nickel-iron multicomponent alloy concentrate, comprising the following steps:

step A, carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomeration agent;

and step B, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate.

In some embodiments of the invention, in step a, the metal agglomeration agent comprises at least one of iron powder, cobalt-nickel-iron multi-alloy concentrate or fine iron powder.

It should be noted that the metal agglomeration agent can be adsorbed on the surface of the fine particles by utilizing the magnetic neutralization effect between the magnetism of the metal agglomeration agent and the fine particles, and can be used for trapping the newly generated ultra-fine metal or alloy; meanwhile, the migration and slag dissociation of newly-generated metal or alloy particles are promoted, so that magnetic concentrate with large particles, high magnetism, low inclusion rate and easy magnetic separation is formed. The metal agglomeration agent is typically, but not limited to, iron powder, cobalt-nickel-iron multi-element alloy concentrate or fine iron powder.

The iron powder refers to reduced iron powder, and the fine iron powder refers to mineral powder obtained by crushing, grinding, and beneficiation of iron ore.

In some preferred embodiments of the present invention, the metal agglomerating agent is added in an amount of 5 to 30% by mass of the cobalt-manganese multi-metal oxide fine ore.

The addition amount of the metal agglomerating agent influences the collecting efficiency and the metal nucleation speed, but the excessive addition of the metal agglomerating agent influences the temperature of a metallurgical bed layer and increases the energy consumption. The metal agglomeration agent is typically, but not limited to, 10%, 15%, 20%, or 25% by weight.

In a preferred embodiment of the present invention, in step a, the metallization reduction roasting is reduced by using a reducing agent, and the reducing agent can convert a positive metal compound into a simple metal. In a preferred embodiment of the invention, the reducing agent comprises a first reducing agent and optionally a second reducing agent.

The above "optional" means that the reducing agent is only the first reducing agent, and may be a mixture of the first reducing agent and the second reducing agent.

The first reductant comprises pulverized coal and/or coke powder.

The term "and/or" means that the first reducing agent can be any one of coal powder or coke powder or a mixture of the coal powder and the coke powder.

The second reducing agent comprises at least one of carbon powder, carbon monoxide, hydrogen, coal gas or natural gas;

the term "at least one" means that the second reducing agent may be any one of carbon powder, carbon monoxide, hydrogen, coal gas or natural gas, or a mixture of any combination thereof.

In a preferable scheme of the invention, the addition amount of the reducing agent is 2-15% of the total mass of the cobalt-manganese multi-metal oxide ore. It should be noted that the addition amount of the reducing agent affects the beneficiation efficiency of the cobalt-manganese multi-metal oxide ore. The amount of reducing agent added is typically, but not limited to, 2%, 4%, 5%, 6%, 8% or 10%.

In a preferred embodiment of the present invention, in the step a, the mixture further includes a certain proportion of a metallization aid. The metallization auxiliary agent can promote the metal reduction reaction and accelerate the reaction rate. The metallization auxiliary agent is at least one of fluoride, sulfide, sulfate and silicon dioxide; the fluoride is at least one of calcium fluoride, magnesium fluoride and sodium fluoride; the sulfide is at least one of pyrite, nickel sulfide ore, copper sulfide ore and synthetic nickel cobalt sulfide; the sulfate is at least one of calcium sulfate, magnesium sulfate and sodium sulfate.

In a preferable scheme of the invention, the addition amount of the metallization auxiliary agent is not more than 10% of the total mass of the cobalt-manganese multi-metal oxide ore. It should be noted that an excessive amount of the metallization promoter may inhibit the metal reduction reaction and affect the metal nucleation. The amount of metallization aids added is typically, but not limited to, 1%, 2%, 2.5%, 3%, 4%, 4.5%, 5%, or 6%.

In a preferred embodiment of the present invention, the mixture in step a may be pressed into pellets.

In order to ensure the uniform distribution of the metal agglomerating agent in the mixture and the air permeability of the materials in the reaction furnace, the mixture needs to be pressed into pellets. The pellets have a diameter of 18-22mm, typically but not limited to, 18mm, 20mm or 22 mm.

In a preferred scheme of the invention, in the step A, the temperature of the metallization reduction roasting is 400-1200 ℃; preferably, the temperature of the metallization reduction roasting is 900 ℃ to 1150 ℃.

The metallization reduction firing is carried out at high temperatures. The temperature change plays a decisive role in the reduction roasting. The temperature is too low, the reduction reaction is less, the reduction degree of metal is low, and the reaction time is long; too high a temperature causes excessive consumption of energy and reduces the capacity of the roaster. In some preferred embodiments of the invention, the temperature of the metallization-reduction firing is typically, but not limited to, 1000 ℃, 1050 ℃, 1100 ℃ or 1150 ℃.

In some embodiments of the invention, the cobalt manganese multimetallic oxide composition used is typically, but not limited to, 1.24% nickel, 0.23% cobalt, 0.82% copper, 6.3% iron, 26.04% manganese, in other embodiments, 0.52% nickel, 0.68% cobalt, 0.13% copper, 14.38% iron, 19.55% manganese, and in still other embodiments, 1.04% cobalt manganese, 0.18% cobalt, 0.87% copper, 5.8% iron, 24.04% manganese, or 0.43% nickel, 0.6% cobalt, 0.058% copper, 15.26% iron, 19.61% manganese.

In some embodiments of the invention, the cobalt-nickel-iron multi-element alloy concentrate is a material of an alloy powder containing more than one of cobalt, nickel and iron and at least iron.

The cobalt-nickel-iron multi-element alloy concentrate is a cobalt-nickel-iron multi-element alloy concentrate, which is obtained by processing a material with low cobalt-nickel-iron alloy grade through a mineral separation process to obtain a certain yield of a material with high cobalt-nickel-iron grade, wherein the part of the material enriched with cobalt-nickel-iron in an alloy form is the cobalt-nickel-iron multi-element alloy concentrate.

In a preferred embodiment of the present invention, the particle size of the fine ore is less than 0.25mm, so as to facilitate the uniform subsequent mixing with the metal agglomerating agent, especially when the particle size of the fine ore is less than 0.074mm and accounts for more than 80%, the subsequent mixing with the metal agglomerating agent is more uniform. It should be noted that the particle size of the fine ore affects the original air permeability of the sinter mix layer, and affects the sintering speed and sintering productivity.

In some embodiments of the invention, in the step B, the magnetic separation is performed on the reduced cobalt-manganese polymetallic oxidized ore, and the magnetic field intensity of the magnetic separation is 100mT to 1000 mT.

Magnetic separation is a mineral separation method that uses the difference in magnetism (magnetic permeability and magnetic susceptibility) of the materials being separated to separate the minerals in the magnetic field of a magnetic separator. The appropriate magnetic field strength can be selected according to the magnetism of the sorted minerals. The magnetic field strength is typically, but not limited to, 200mT, 250mT, 400mT, 500mT or 600 mT.

In a third aspect of the present invention, the present invention provides a solid-phase metallization reduction-based cobalt-manganese multi-metal oxide ore dressing and metallurgy combination method, wherein step a is the same as step a in the preparation method of the cobalt-nickel-iron multi-element alloy provided by the present invention, and the corresponding embodiments and preferred schemes are the same, which are not described herein again, except that the present invention further includes steps b and c after step a, which are specifically as follows: b, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate and manganese-enriched manganese concentrate;

c, separating and recovering cobalt and nickel from the cobalt-nickel-iron multicomponent alloy concentrate;

the metal agglomerating agent in the step a is the cobalt-nickel-iron multi-element alloy concentrate or the cobalt-nickel-iron multi-element alloy concentrate prepared by the preparation method of the cobalt-nickel-iron multi-element alloy concentrate in the second aspect of the invention.

The magnetic separation in step b of the present invention is the same as the magnetic separation in step b of the second aspect of the present invention, and the preferred embodiment is the same, and will not be described herein again.

In a preferred scheme of the invention, the cobalt-nickel-iron multicomponent alloy concentrate enriched with cobalt and nickel is pulped by using a leaching agent, leached and then purified and separated, and cobalt and nickel are recovered.

Lixiviant refers to a chemical agent that selectively and relatively completely dissolves the metal species in the concentrate into solution. Then, the metal substance can be obtained through liquid-solid separation, solution purification, metal extraction in the solution and wastewater treatment.

In a preferred mode of the present invention, the leaching agent includes at least one of a sulfuric acid solution, a hydrochloric acid solution, or an ammonia solution.

The "at least one" means that the leaching agent may be any one of a sulfuric acid solution, a hydrochloric acid solution, and an ammonia solution, or may be a mixed solution of any two or more. The ammoniacal solution means ammonia water, an ammonium salt or a mixed solution of the two.

The invention takes the cobalt-nickel-iron multi-component alloy concentrate as the metal agglomerating agent in the cobalt-manganese multi-metal oxide ore dressing and smelting combined method, is beneficial to promoting the alloy to agglomerate at a lower temperature, avoids mutual adhesion and kiln bonding of roasted materials, and can improve the grade of cobalt and nickel in the cobalt-nickel-iron multi-component alloy concentrate.

The preparation method of the cobalt-nickel-iron multi-element alloy provided by the invention has the advantages of simple process, small post-treatment amount, high recovery rate, low energy consumption, low cost and good environmental protection.

According to the cobalt-manganese multi-metal oxide ore dressing-smelting combined method based on solid-phase metallization reduction, nickel, cobalt and iron in the ore are selectively reduced into metal through high-temperature reduction roasting, magnetic cobalt-nickel-iron multi-element alloy is obtained through reduction roasting and is subjected to magnetic separation, manganese concentrate and cobalt-nickel-iron multi-element alloy concentrate are obtained, subsequent smelting treatment amount is reduced, and purification and impurity removal procedures are simplified.

The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

Example 1

The embodiment provides a preparation method of a cobalt-nickel-iron multi-element alloy concentrate, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.24% of nickel, 0.23% of cobalt, 0.82% of copper, 6.3% of iron and 26.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 80%, thereby preparing fine ore.

And 2, uniformly mixing the fine ore prepared in the step 1, anthracite accounting for 5% of the total mass of the cobalt-manganese multi-metal oxide ore and 25% of nucleation iron powder, adding a certain amount of water, and pressing into pellets with the diameter of 20 mm.

And 3, drying and preheating the pellets prepared in the step 2, then transferring the pellets into a closed heating furnace for metallized reduction roasting at 1150 ℃ for 2.5h, and cooling the reduction roasted material to obtain a cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 10.55, 1.98, 7.11, 12.88, 56.86; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 74.02, 74.90, 75.44, 4.30, 78.52.

Example 2

This embodiment provides a method for preparing a cobalt-nickel-iron multi-element alloy concentrate, which is used to process cobalt-manganese multi-metal oxide ores containing 1.04% of nickel, 0.18% of cobalt, 0.87% of copper, 5.8% of iron, and 24.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 90%, thereby preparing fine ore.

And 2, mixing the fine ore prepared in the step 1, 20% of nucleation iron powder and 2% of coke powder to form a mixture.

And 3, transferring the mixture prepared in the step 2 into a closed heating furnace, introducing hydrogen gas atmosphere with the mass of 10% of the total mass of the cobalt-manganese multi-metal oxide ores, carrying out metallization reduction roasting for 3 hours at 1000 ℃, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 400mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 8.88, 1.62, 7.38, 10.20, 57.01; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 68.31, 76.24, 67.86, 3.42, 78.63.

Example 3

The embodiment provides a preparation method of a cobalt-nickel-iron multi-element alloy concentrate, which is a cobalt-manganese multi-metal oxide ore dressing and smelting combined method based on solid-phase metallization reduction, and is used for treating cobalt-manganese multi-metal oxide ores containing 1.04% of nickel, 0.18% of cobalt, 0.87% of copper, 5.8% of iron and 24.04% of manganese, and the method can comprise the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 90%, thereby preparing fine ore.

And 2, mixing the fine ore prepared in the step 1, 10% of nucleation iron powder, 5% of calcium fluoride, 5% of pyrite and 4% of coke powder to form a mixture.

And 3, transferring the mixture prepared in the step 2 into a closed heating furnace, introducing hydrogen gas atmosphere with the mass of 10% of the total mass of the cobalt-manganese multi-metal oxide ores, carrying out metallization reduction roasting for 3.5 hours at 1000 ℃, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 8.9, 1.44, 7.18, 11.54, 56.63; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 74.45, 73.69, 71.80, 4.21, 84.95.

Example 4

The embodiment provides a preparation method of a cobalt-nickel-iron multi-element alloy concentrate, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.24% of nickel, 0.23% of cobalt, 0.82% of copper, 6.3% of iron and 26.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 80%, thereby preparing fine ore.

And 2, uniformly mixing the fine ore prepared in the step 1 with anthracite, 3% sodium fluoride, 6% sodium sulfate, 2.5% silicon dioxide and 25% nucleation iron powder which account for 5% of the total mass of the cobalt-manganese multi-metal oxide ore, adding a certain amount of water, and pressing into pellets with the diameter of 20 mm.

And 3, drying and preheating the pellets prepared in the step 2, then transferring the pellets into a closed heating furnace for metallized reduction roasting at 1100 ℃ for 2.5 hours, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 250mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 10.23, 1.65, 6.98, 12.33, 57.13; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 71.78, 62.41, 74.06, 4.12, 78.89.

Example 5

This embodiment provides a cobalt-manganese multi-metal oxide ore dressing-smelting combined method based on solid-phase metallization reduction, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.24% of nickel, 0.23% of cobalt, 0.82% of copper, 6.3% of iron, and 26.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 80%, thereby preparing fine ore.

And 2, uniformly mixing the fine ore prepared in the step 1, anthracite accounting for 5% of the total mass of the cobalt-manganese multi-metal oxide ore and 25% of nucleation iron powder, adding a certain amount of water, and pressing into pellets with the diameter of 20 mm.

And 3, drying and preheating the pellets prepared in the step 2, then transferring the pellets into a closed heating furnace for metallized reduction roasting at 1150 ℃ for 2.5h, and cooling the reduction roasted material to obtain a cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

And 5, returning 25% of the cobalt-nickel-iron multi-element alloy concentrate obtained in the step 4 to the step 2 for mixing.

And 6, slurrying and leaching the 75% of cobalt-nickel-iron multi-element alloy concentrate remaining in the step 5 by using a sulfuric acid solution or a hydrochloric acid solution or an ammonia solution, and then purifying and separating to recover cobalt and nickel.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 10.77, 2.02, 6.66, 7.89, 51.24; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 95.54, 96.61, 89.34, 3.33, 89.47.

Example 6

This embodiment provides a cobalt-manganese multi-metal oxide ore dressing and metallurgy combined method based on solid-phase metallization reduction, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.04% of nickel, 0.18% of cobalt, 0.87% of copper, 5.8% of iron, and 24.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 90%, thereby preparing fine ore.

And 2, mixing the fine ore prepared in the step 1, 20% of nucleation iron powder and 2% of coke powder to form a mixture.

And 3, transferring the mixture prepared in the step 2 into a closed heating furnace, introducing hydrogen gas atmosphere with the mass of 10% of the total mass of the cobalt-manganese multi-metal oxide ores, carrying out metallization reduction roasting for 3 hours at 1000 ℃, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 400mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

And 5, returning 20% of the cobalt-nickel-iron multi-element alloy concentrate obtained in the step 4 to the step 2 for mixing.

And 6, slurrying and leaching the residual 80% of cobalt-nickel-iron multicomponent alloy concentrate obtained in the step 5 by using a sulfuric acid solution or a hydrochloric acid solution or an ammonia solution, and then purifying and separating to recover cobalt and nickel.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 9.13, 1.50, 7.34, 5.22, 67.33; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 94.81, 95.29, 91.12, 2.36, 86.57.

Example 7

This embodiment provides a cobalt-manganese multi-metal oxide ore dressing and metallurgy combined method based on solid-phase metallization reduction, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.04% of nickel, 0.18% of cobalt, 0.87% of copper, 5.8% of iron, and 24.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 90%, thereby preparing fine ore.

And 2, mixing the fine ore prepared in the step 1, 10% of nucleation iron powder, 5% of calcium fluoride, 5% of pyrite and 4% of coke powder to form a mixture.

And 3, transferring the mixture prepared in the step 2 into a closed heating furnace, introducing hydrogen gas atmosphere with the mass of 10% of the total mass of the cobalt-manganese multi-metal oxide ores, carrying out metallization reduction roasting for 3.5 hours at 1000 ℃, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

And 5, returning 10% of the cobalt-nickel-iron multi-element alloy concentrate obtained in the step 4 to the step 2 for mixing.

And 6, slurrying and leaching the residual 90% of cobalt-nickel-iron multicomponent alloy concentrate obtained in the step 5 by using a sulfuric acid solution or a hydrochloric acid solution or an ammonia solution, and then purifying and separating to recover cobalt and nickel.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 9.09, 1.42, 6.99, 7.85, 65.83; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 96.14, 91.88, 88.38, 3.62, 86.21.

Example 8

This embodiment provides a cobalt-manganese multi-metal oxide ore dressing-smelting combined method based on solid-phase metallization reduction, which is used for treating cobalt-manganese multi-metal oxide ores containing 1.24% of nickel, 0.23% of cobalt, 0.82% of copper, 6.3% of iron, and 26.04% of manganese, and may include the following steps:

step 1, crushing and grinding the cobalt-manganese multi-metal oxide ore until the granularity is less than 0.074mm and accounts for more than 80%, thereby preparing fine ore.

And 2, uniformly mixing the fine ore prepared in the step 1 with anthracite, 3% sodium fluoride, 6% sodium sulfate, 2.5% silicon dioxide and 25% nucleation iron powder which account for 5% of the total mass of the cobalt-manganese multi-metal oxide ore, adding a certain amount of water, and pressing into pellets with the diameter of 20 mm.

And 3, drying and preheating the pellets prepared in the step 2, then transferring the pellets into a closed heating furnace for metallized reduction roasting at 1100 ℃ for 2.5 hours, and cooling the reduction roasted material to obtain the cooled material.

And 4, crushing and grinding the cooled material obtained in the step 3, and then carrying out magnetic separation in a field intensity of 250mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate.

And 5, returning 25% of the cobalt-nickel-iron multi-element alloy concentrate obtained in the step 4 to the step 2 for mixing.

And 6, slurrying and leaching the 75% of cobalt-nickel-iron multi-element alloy concentrate remaining in the step 5 by using a sulfuric acid solution or a hydrochloric acid solution or an ammonia solution, and then purifying and separating to recover cobalt and nickel.

The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 10.65, 1.93, 6.42, 9.86, 50.21; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 94.48, 92.30, 86.12, 4.17, 87.67.

The cobalt-manganese multi-metal oxide ore used in the following comparative examples has the same composition and preparation method of fine ore, and is not repeated herein. The preparation method of the cobalt-manganese multi-metal oxide ore and the fine ore comprises the following steps:

the method comprises the steps of treating cobalt-manganese multi-metal oxide ores containing 1.04% of nickel, 0.17% of cobalt, 0.87% of copper, 5.8% of iron and 23.84% of manganese, crushing and grinding the cobalt-manganese multi-metal oxide ores until the granularity is smaller than 0.074mm and accounts for more than 80%, and thus obtaining fine ores.

Comparative example 1

Uniformly mixing the fine ore with anthracite, calcium fluoride and silicon dioxide which account for 7 percent of the total mass of the cobalt-manganese multi-metal oxide ore, 4 percent of the total mass of the cobalt-manganese multi-metal oxide ore and 5 percent of the total mass of the cobalt-manganese multi-metal oxide ore, adding a certain amount of water, and pressing the mixture into pellets with the diameter of 20 mm; after drying and preheating treatment, the pellets are transferred into a closed heating furnace to be metallized, reduced and roasted for 2.5 hours at 1050 ℃, and the material after reduction roasting is cooled, so that the cooled material is obtained; and crushing and grinding the cooled material, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate. The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 9.39, 1.56, 7.68, 7.52, 55.04; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 72.23, 73.41, 70.62, 2.52, 75.92.

Comparative example 2

Uniformly mixing the fine ore with anthracite, 4% calcium fluoride, 5% silicon dioxide and 6% ferrous sulfide which account for 7% of the total mass of the cobalt-manganese multi-metal oxide ore, adding a certain amount of water, and pressing into pellets with the diameter of 20 mm; after drying and preheating treatment, the pellets are transferred into a closed heating furnace to be metallized, reduced and roasted for 2.5 hours at 1050 ℃, and the material after reduction roasting is cooled, so that the cooled material is obtained; and crushing and grinding the cooled material, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate. The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 6.16, 1.01, 5.0, 9.19, 58.2; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 86.48, 86.74, 83.91, 5.63, 88.42.

Comparative example 3

Uniformly mixing the fine ore with anthracite, calcium fluoride, silicon dioxide and nucleation iron powder which account for 7 percent of the total mass of the cobalt-manganese multi-metal oxide ore, 4 percent of the total mass of the cobalt-manganese multi-metal oxide ore, adding a certain amount of water, and pressing the mixture into pellets with the diameter of 20 mm; after drying and preheating treatment, the pellets are transferred into a closed heating furnace to be metallized, reduced and roasted for 2.5 hours at 1050 ℃, and the material after reduction roasting is cooled, so that the cooled material is obtained; and crushing and grinding the cooled material, and then carrying out magnetic separation in a field intensity of 200mT to obtain the cobalt-nickel-iron multi-element alloy concentrate and the manganese concentrate. The grades of nickel, cobalt, copper, manganese and iron in the cobalt-nickel-iron multi-element alloy concentrate are (%): 9.22, 1.52, 7.21, 4.19, 69.85; the recovery rates of nickel, cobalt, copper, manganese and iron were (%): 95.75, 96.56, 89.50, 1.90, 89.81.

According to the comparative example, in the comparative example 1, under the condition that no metal sulfide and crystal nucleus exist, the yield of the magnetic separation cobalt-nickel-iron multi-element alloy concentrate is low although the grade is high, so that the recovery rate of valuable metals is low; compared with the prior art, the metal sulfide is added in the comparative example 2, so that the recovery rate of valuable metals is improved, the yield is greatly increased, the metal grade of the magnetic separation cobalt-nickel-iron multi-element alloy concentrate is reduced, and the treatment capacity is increased; compared with the prior art, after the metallization crystal nucleus is added in the comparative example 3, the recovery rate of valuable metals can be obviously improved under the condition of keeping the metal grade of the magnetic separation cobalt-nickel-iron multi-element alloy concentrate.

While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.

Claims (16)

1. The cobalt-nickel-iron multi-element alloy concentrate is used as a metal agglomerating agent in the dressing and smelting of cobalt-manganese multi-metal oxide ores.

2. The preparation method of the cobalt-nickel-iron multicomponent alloy concentrate is characterized by comprising the following steps of:

step A, carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomeration agent;

and step B, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate.

3. The method of claim 2, wherein in step a, the metal agglomeration agent comprises at least one of iron powder, cobalt-nickel-iron multi-element alloy concentrate or fine iron powder.

4. The method for preparing the cobalt-nickel-iron multi-element alloy concentrate according to claim 2, wherein the addition amount of the metal agglomerating agent is 5-30% of the mass of the cobalt-manganese multi-metal oxide ore powder.

5. The method for preparing the cobalt-nickel-iron multi-element alloy concentrate according to claim 2, wherein in the step A, the metallization reduction roasting is reduced by using reducing agents, and the reducing agents comprise a first reducing agent and an optional second reducing agent;

wherein the first reducing agent comprises pulverized coal and/or coke powder;

the second reducing agent comprises at least one of carbon powder, carbon monoxide, hydrogen, coal gas or natural gas.

6. The method for preparing the cobalt-nickel-iron multi-element alloy concentrate according to claim 5, wherein the addition amount of the reducing agent is 2-15% of the total mass of the cobalt-manganese multi-metal oxide ore.

7. The method for preparing the cobalt-nickel-iron multicomponent alloy concentrate according to claim 2, wherein in the step A, the mixture further comprises a metallization aid.

8. The method of claim 7, wherein the metallization aid comprises at least one of fluoride, sulfide, sulfate, or silica.

9. The method for preparing the cobalt-nickel-iron multi-element alloy concentrate according to claim 7, wherein the addition amount of the metallization promoter is not more than 10% of the total mass of the cobalt-manganese multi-metal oxide ore.

10. The method for preparing the cobalt-nickel-iron multicomponent alloy concentrate according to claim 2, wherein in the step A, the temperature of the metallization-reduction roasting is 400-1200 ℃.

11. The method for preparing the cobalt-nickel-iron multicomponent alloy concentrate according to claim 2, wherein the temperature of the metallization reduction roasting is 900 ℃ to 1150 ℃.

12. The method of claim 2, wherein in the step A, the powdered Co-Mn-Mo-O-alloy ore comprises at least one of a powdered seafloor multi-metal nodule ore, a powdered seafloor cobalt-rich crust ore, or a powdered land-based multi-Mo-O-Mn ore.

13. The method of claim 2, wherein the cobalt-nickel-iron multi-alloy concentrate comprises iron, optionally cobalt, and optionally nickel.

14. The method for preparing the cobalt-nickel-iron multi-element alloy concentrate according to claim 2, wherein in the step A, the granularity of the cobalt-manganese multi-metal oxidized ore powder is less than 0.25 mm.

15. The method for preparing the cobalt-nickel-iron multicomponent alloy concentrate according to claim 2, wherein in the step B, the magnetic field intensity of the magnetic separation is 100 mT-1000 mT.

16. A cobalt-manganese multi-metal oxide ore dressing and smelting combined method based on solid-phase metallization reduction is characterized by comprising the following steps:

step a, carrying out metallization reduction roasting on a mixture of cobalt-manganese multi-metal oxide ore powder and a metal agglomeration agent;

b, carrying out magnetic separation on the material subjected to the metallization reduction roasting to obtain cobalt-nickel-enriched cobalt-nickel-iron multi-element alloy concentrate and manganese-enriched manganese concentrate;

c, separating and recovering cobalt and nickel from the cobalt-nickel-iron multicomponent alloy concentrate;

wherein, the metal agglomerating agent in the step a comprises the cobalt-nickel-iron multi-component alloy concentrate in the claim 1 or the cobalt-nickel-iron multi-component alloy concentrate prepared by the preparation method of any one of the claims 2 to 15.