CN115094245A - Method for synchronously recycling cobalt and iron from low-cobalt multi-metal sulfide ore - Google Patents

Method for synchronously recycling cobalt and iron from low-cobalt multi-metal sulfide ore Download PDF

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CN115094245A
CN115094245A CN202210716221.3A CN202210716221A CN115094245A CN 115094245 A CN115094245 A CN 115094245A CN 202210716221 A CN202210716221 A CN 202210716221A CN 115094245 A CN115094245 A CN 115094245A
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cobalt
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CN115094245B (en
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周友连
魏祥松
黄雷鸣
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Geologychina Research Institute Of Chemical Geolgy And Mine Bureau
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/023—Obtaining nickel or cobalt by dry processes with formation of ferro-nickel or ferro-cobalt
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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Abstract

The invention relates to the technical field of recovery and extraction of valuable metals by combining ore dressing and metallurgy, in particular to a method for synchronously recovering cobalt and iron from low-cobalt polymetallic sulfide ores. The method is based on the basic characteristics of the low-cobalt multi-metal sulphide ore, and provides the method for extracting the cobalt and the iron in the low-cobalt multi-metal sulphide ore by adopting a weak oxygen roasting-solid reduction process after deep research; wherein, the cobalt-sulfur concentrate obtained by flotation is roasted by weak oxygen, so that the main mineral is subjected to ore phase reconstruction, and mineralogical conditions are created for cobalt-iron separation; then, carrying out magnetic separation to enrich the product obtained by weak oxygen roasting again to obtain cobalt-iron concentrate; the characteristics that the cobalt content in the cobalt-iron concentrate is low, the iron content is high and the cobalt-iron concentrate can be reduced to a metal state are skillfully utilized, and the cobalt-iron solid solution product is obtained by recovering and extracting the metal cobalt by taking the metal iron as a carrier through reduction roasting.

Description

Method for synchronously recycling cobalt and iron from low-cobalt multi-metal sulfide ore
Technical Field
The invention belongs to the technical field of mineral separation-metallurgy combined recovery and extraction of valuable metals, and particularly relates to a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores.
Background
The polymetallic sulphide ore contains a plurality of useful elements, wherein the main elements are iron, copper, lead, zinc, sulfur and the like, and meanwhile, valuable elements such as cobalt, nickel, silver, cadmium and the like are associated.
For some low-cobalt multi-metal sulfide ores with low cobalt content (the average grade is only 0.02%), lead, zinc, copper and other elements in the low-cobalt multi-metal sulfide ores are mainly recovered in a multi-stage flotation mode, and cobalt and iron in the low-cobalt multi-metal sulfide ores are not recycled, so that huge waste of resources is caused.
Generally, because the occurrence state of minerals in cobalt-containing ores is complex, the selectivity difference is large, and it is difficult to directly obtain cobalt products only by adopting a flotation process, the cobalt-containing ores are usually subjected to flotation, and cobalt concentrates obtained by flotation are further separated to extract cobalt. The technical method for extracting cobalt from the cobalt concentrate is various, and the process flow is usually long. The existing processes can be divided into three major categories according to the production method: (1) the cobalt is primarily enriched by pyrometallurgical pretreatment, and then the cobalt product is purified by leaching to remove impurities. (2) Directly adopts a wet process to extract cobalt. (3) And (4) leaching the microorganisms.
The common representative cobalt extraction process is as follows:
the method comprises the steps of adding a reducing agent or a vulcanizing agent into cobalt-containing converter slag, cobalt oxide ore or arsenic-cobalt ore, reducing Ni, Co, Fe and the like in raw materials into metal by controlling the reduction degree in the high-temperature smelting process, leaving most of Fe oxide in the slag to obtain Co, Ni and Fe alloy or cobalt sulfonium, and finally obtaining a cobalt product by dissolving, purifying and removing impurities.
After sulfating roasting, leaching to extract cobalt, which is to perform sulfating roasting on pyrite containing cobalt to generate SO 2 The metal sulfide in the ore generates corresponding intermediate sulfate. Because the decomposition temperature of ferric sulfate is lower than that of cobalt sulfate, nickel and copper, the ferric sulfate is decomposed into Fe by controlling the air volume and the roasting temperature 2 O 3 Co, Ni and Cu exist in the cinder in a sulfate state, and the cinder is leached by dilute acid to obtain a cobalt-containing solution. Then purifying, extracting and precipitating cobalt to obtain a cobalt product.
The reductive roasting ammonia leaching process includes the steps of leaching the material containing Co and NiThe oxidized ore is first reduced and roasted, the cobalt and nickel in the oxidized ore are reduced to metallic state, and the iron is reduced to magnetic iron oxide. Then the calcine obtained by reduction is put in NH 3 -CO 2 -H 2 And carrying out normal pressure leaching in an O system. The cobalt, nickel and ammonia complexes go together into solution under oxidizing conditions, while the iron ammonia complex is oxidized and hydrolyzed to the hydroxide precipitate.
Although the three traditional processes are mature in technology, the problems of low resource utilization rate, large reagent consumption, long flow, easy environmental pollution and the like exist in the leaching section.
A pressure direct leaching method for preparing 45% concentration ore pulp from laterite ore and the metallic sulfide in ore concentrate and O dissolved in solution under a certain pressure and temp 2 、NH 3 、H 2 O reacts, Ni, Co and Cu generate soluble ammonia complexes to enter the solution, and Fe generates insoluble Fe 2 O 3 And remaining in the leached residue. The method has the advantages of high selective leaching rate of target metal, low leaching rate of impurity metal iron and mature process, but the method has strict requirements on the working conditions of equipment, and the application of the method is influenced by easy scaling of a reactor.
The microbial leaching method, Young as early as 50 years in the last century, firstly proposed the concept of leaching cobalt-containing minerals by using bacteria. The scholars at home and abroad use bacteria such as thiobacillus ferrooxidans, thiobacillus thiooxidans and leptospirillum ferrooxidans to carry out the process and mechanism research of microbial leaching of various cobalt-containing minerals. The method has mild conditions, easy operation and environmental protection, and has great advantages for processing low-grade and difficultly processed mineral resources. However, the culture and propagation of bacteria in the method are limited by objective conditions of the environment, the leaching rate is slow, and the leaching period is long, so that the large-scale application of the method is limited.
Many researchers improve and innovate on the basis of the cobalt extraction method, for example, for complex cobalt-sulfur concentrates in the Panxi area, a cobalt concentrate product with the cobalt grade of 18.2% and the cobalt recovery rate of 83.4% can be obtained by recovering cobalt by an oxidizing roasting-sulfidizing flotation method, and then further separation and extraction of cobalt are still needed. If aiming at the defects of the pressure leaching process, the mineral structure is destroyed by concentrated sulfuric acid under the condition of adding an accelerant, corresponding sulfate is generated, and the separation of impurities such as nickel, cobalt and iron is realized through water leaching separation, although the leaching rate of nickel and cobalt is improved, the obtained final product is not cobalt, and the extraction process is still longer. Aiming at the slow leaching rate of microorganisms, researchers adopt Tween-20, Tween-80 catalysts and active carbon to promote the biological leaching of cobalt concentrate, and the cobalt leaching rate can be improved by 20.50%. Although the method improves the leaching rate of cobalt, the method also has the problems of long leaching period and limited culture and propagation of bacteria.
In summary, the research developed for recycling cobalt in the cobalt-containing minerals has the problems that the existing state of the minerals is complex, and the adopted pyrometallurgical or wet leaching process has long process flow, high production cost, low recovery rate, environment friendliness and the like after the cobalt-containing concentrate is obtained through flotation.
For low-grade multi-metal sulfide ores, the ores are generally wrapped and have uneven embedded particle sizes, so that the leaching of target ore cobalt is not facilitated. The multi-metal sulfide ore contains more metal elements, has low cobalt content and complex occurrence state, and has quite complicated extraction and purification process sections, longer corresponding process flow and more required supporting equipment; and the types of the adopted extracting agents are various, and if the extracting agents are not recovered properly, the environment can be polluted. Therefore, the traditional cobalt recovery technology is adopted to recover the cobalt in the low-cobalt polymetallic sulphide ore, so that the economic benefit is poor.
Therefore, if a new efficient clean recovery process for cobalt in low-grade multi-metal sulphide ore can be developed, the cobalt in the multi-metal sulphide ore can be economically and efficiently recovered and utilized, and a new way can be provided for the recovery and utilization of the similar cobalt resource.
Disclosure of Invention
The invention provides a novel method for synchronously extracting cobalt and iron from low-cobalt multi-metal sulphide ores, aiming at solving the problems in the process of recovering and extracting cobalt from the low-estimation multi-metal sulphide ores. The method has the advantages of relatively simple process, high comprehensive economic benefit, high cobalt and iron recovery rate of over 65 percent and the like.
The invention provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
s1, pre-enriching by flotation to obtain cobalt-sulfur concentrate;
s2, roasting the obtained cobalt-sulfur concentrate with weak oxygen to obtain oxides containing cobalt and iron;
s3, carrying out magnetic separation on the oxide containing cobalt and iron to obtain cobalt and iron concentrate, and then carrying out reduction roasting on the obtained cobalt and iron concentrate to obtain a cobalt and iron metal solid solution product.
The invention starts from the basic characteristics of low-cobalt multi-metal sulphide ore, and provides the improvement of the form of the extracted product for the first time in the industry after intensive research, namely, the invention overcomes the technical bias of the product form of separately recovering cobalt in the field and provides the product form of the cobalt-iron metal solid solution with metal iron as a carrier to load metal cobalt.
In order to realize the new extraction form, the invention adopts a weak oxygen roasting-solid reduction process to extract cobalt and iron in the low-cobalt polymetallic sulphide ore; the obtained cobalt-sulfur concentrate is roasted by weak oxygen, so that the main mineral is subjected to ore phase reconstruction, the grade of cobalt is improved, a reduction basis is provided for the follow-up process, and mineralogical conditions are created for cobalt-iron separation; performing magnetic separation to enrich the target minerals obtained by weak oxygen roasting again to obtain cobalt-iron concentrate; and further skillfully utilizing the characteristics that the cobalt content in the cobalt-iron concentrate is low, the iron content is high, and the cobalt-iron concentrate can be reduced to be in a metal state, and recovering and extracting the metal cobalt by taking the metal iron as a carrier through reduction roasting to obtain a cobalt-iron metal solid solution product.
As known to those skilled in the art, mineral separation and extraction technology is based on the difference of physical properties (particle size, density, magnetism, surface electrical property, surface hydrophilic or hydrophobic property, etc.) and chemical properties (oxidation, reduction, etc.) of minerals to achieve the purpose of separation and extraction.
However, the low cobalt polymetallic sulphide mineral phase composition is more complex than other conventional minerals, mainly based on minerals such as pyrite, pyrrhotite, blende, galena, chalcopyrite, quartz, dolomite, biotite, etc., and wherein the cobalt replaces the iron in pyrite and pyrrhotite mainly in a homogeneous like manner. In addition, the prior art does not study the physical properties and the chemical properties of the low-cobalt multi-metal sulphide ore, and particularly studies the relation between the physicochemical properties and the separation and extraction effects of the low-cobalt multi-metal sulphide ore. Therefore, how to efficiently extract high-grade cobalt-iron solid solution from the complex mineral is difficult to determine a proper extraction process through reasoning or logic analysis only by virtue of common sense, and therefore, the specific recovery extraction process adopted by the application aiming at the low-cobalt multi-metal sulphide ore mineral is not obvious compared with the prior art.
Further, in S1, cobalt-sulfur concentrate enriched in cobalt is obtained by flotation; the cobalt-sulfur concentrate is a sulfide ore concentrate, and the main components of the cobalt-sulfur concentrate are pyrite and pyrrhotite.
The adopted flotation reagents comprise collecting agents, inhibitors, regulators, activators and foaming agents.
The collecting agent is one of xanthate or black powder; inhibitors include, but are not limited to, sulfites, citrates; modifiers include, but are not limited to, caustic soda, lime, soda ash, sulfuric acid; activators include, but are not limited to, metal sulfates; foaming agents include, but are not limited to, No. two oil, turpentine.
The addition amounts of the collecting agent, the inhibitor, the regulator, the activator and the foaming agent are respectively 50g/t-250g/t, 25g/t-150g/t, 600g/t-1000g/t, 25g/t-100g/t and 0g/t-100 g/t. The method can be specifically adjusted and optimized by combining with professional common knowledge according to actual needs, as long as the quality of the obtained target product cobalt-sulfur concentrate can be ensured.
Further, in S2, the conditions of the weak oxygen roasting are: the oxygen concentration is 5-25%, the roasting temperature is 600-1050 ℃, and the roasting time is 30-180 min. Research shows that based on the characteristics of flotation products, the ore phase reconstruction effect of the cobalt-sulfur concentrate can be better by reasonably controlling the matching relationship between the oxygen concentration and the roasting temperature, and further, better mineralogical conditions are created for cobalt-iron separation.
Further, the process in S3 is as follows:
(1) carrying out magnetic separation on the target product obtained in the step S2 to obtain cobalt-iron concentrate;
(2) adding an additive into the obtained cobalt-iron concentrate, uniformly mixing, agglomerating, and then carrying out reduction roasting;
(3) and cooling the obtained reduction product, and then carrying out ore grinding-magnetic separation to obtain magnetic minerals, namely the cobalt-iron metal solid solution product.
Wherein, in the step (2), the additive is formed by mixing a plurality of alkali metal salts, including but not limited to sodium carbonate, sodium sulfate, sodium humate, borax and the like; through the action of the additive, the reduction temperature can be greatly reduced, the reduction of cobalt and iron is catalyzed, and the growth of cobalt and iron grains is promoted; meanwhile, the magnetic separation agent can perform chemical reaction with gangue minerals in the cobalt-iron concentrate to generate nonmagnetic substances, destroy the original structure of the minerals, create favorable conditions for synchronously recycling cobalt and iron in the cobalt-iron concentrate and strengthen the separation effect. The total addition amount of the additive is 10-30% of the mass of the obtained cobalt-iron concentrate.
The reducing agent used in the reduction roasting in the step (2) is coal powder, such as high-quality pulverized lignite or anthracite; the reducing roasting conditions are as follows: the temperature is 1000-1100 ℃, and the time is 60-120 min.
Wherein, the magnetic separation condition is as follows: the magnetic field intensity is 800Gs-2000 Gs; and before magnetic separation, the granularity of the mineral in the step (3) needs to be controlled to be-0.074 mm and accounts for more than 80 percent.
In the invention, the Co content in the low-cobalt multi-metal sulphide ore ranges from 0.01 to 0.05 percent, and the average content is 0.02 percent; the content of Fe in the low-cobalt multi-metal sulfide ore is not particularly limited as long as the low-cobalt multi-metal sulfide ore can be used as a carrier to achieve the purpose of loading metal cobalt, and the content of Fe is generally more than 15%. Carrying out flotation on low-cobalt polymetallic sulphide ores to obtain Co-enriched cobalt-sulphur concentrates; then carrying out weak oxygen roasting and magnetic separation to obtain cobalt-iron concentrate further enriched with Co; finally, obtaining the cobalt-iron solid solution product with higher Co content through reduction roasting, ore grinding and magnetic separation.
In addition, before flotation, raw ore is crushed and ground to-200 meshes accounting for more than 80%, and the crushed raw ore powder is mixed uniformly, so that the subsequent flotation effect can be improved.
As one embodiment of the invention, the method for synchronously recovering the cobalt and the iron from the low-cobalt multi-metal sulphide ore comprises the following steps:
the first step is as follows: crushing and grinding the low-cobalt polymetallic sulphide ore raw ore until the crushed raw ore is-200 meshes and accounts for more than 80 percent, and uniformly mixing the crushed raw ore powder;
the second step is that: carrying out flotation on pyrite in low-cobalt polymetallic sulphide ore raw ore, wherein a target product obtained by the flotation is sulphide ore concentrate, and the main components of the sulphide ore concentrate are pyrite and pyrrhotite;
the flotation reagent comprises a collecting agent, an inhibitor, a regulator, an activator and a foaming agent, and the addition amounts of the collecting agent, the inhibitor, the regulator, the activator and the foaming agent are respectively 50g/t-250g/t, 25g/t-150g/t, 600g/t-1000g/t, 25g/t-100g/t and 0g/t-100 g/t;
the third step: drying the cobalt-sulfur concentrate obtained by flotation, and roasting the obtained dry cobalt-sulfur concentrate with weak oxygen to obtain a roasted product which is mainly cobalt-containing iron oxide;
wherein, the oxygen concentration is 5 to 25 percent, the roasting temperature is 600 to 1050 ℃, and the roasting time is 30 to 180 min;
the fourth step: carrying out magnetic separation on the cobalt-containing iron oxide obtained in the third step by adopting a magnetic field intensity of 800Gs-2000Gs to obtain cobalt-iron concentrate;
the fifth step: adding an additive into the cobalt-iron concentrate obtained in the fourth step, uniformly mixing, agglomerating, and carrying out reduction roasting; cooling the reduction product, crushing, grinding until the diameter of minus 0.074mm accounts for more than 80%, and performing magnetic separation by adopting the magnetic field intensity of 800Gs-2000Gs to obtain the magnetic mineral which is a cobalt-iron product;
wherein, coal powder is used as a reducing agent, and is reduced and roasted for 60min to 120min at the temperature of 1000 ℃ to 1100 ℃.
The invention has the following beneficial effects:
1. the process for extracting the cobalt and the iron by the weak oxygen roasting-solid reduction breaks through the limitation of the traditional method of pre-enriching the cobalt by adopting a pyrogenic process and then removing impurities by leaching to purify the cobalt product; compared with the traditional process, the process disclosed by the invention is relatively shorter in flow, less in reagent consumption, less in supporting facilities and less in environmental pollution, and realizes efficient, clean and synchronous recovery of cobalt and iron.
2. The additive in the reduction roasting process can greatly reduce the reduction temperature, catalyze the reduction of cobalt and iron and promote the growth of cobalt and iron grains; meanwhile, the magnetic separation agent can perform chemical reaction with gangue minerals in the cobalt-iron concentrate to generate nonmagnetic substances, destroy the original structure of the minerals, create favorable conditions for synchronously recycling cobalt and iron in the cobalt-iron concentrate and strengthen the separation effect.
3. The cobalt and iron in the cobalt-iron product obtained by the invention have high grade and low impurity content, can be used as high-quality raw materials for separating and extracting cobalt and iron, and can also be directly used as raw materials for preparing iron-cobalt alloy materials, thereby avoiding the waste of energy and resources caused by the processes of first separating cobalt and iron and then fusing cobalt and iron in the process of producing the alloy by adopting a mechanical alloying process or an electrolysis process.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Example 1:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps as shown in fig. 1:
(1) crushing and grinding low-cobalt polymetallic sulphide ore with the Fe content of 36.17% and the Co content of 0.047% to 85% with a grain size of-200 meshes;
(2) and after fine grinding, performing flotation on the sulphide ore in the low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, an adjusting agent is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil and the second oil are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt sulphur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 5%, the roasting temperature is 600 ℃, and the roasting time is 180 min;
(4) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs to obtain cobalt-iron concentrate with the Fe content of 40.21 percent and the Co content of 0.81 percent;
(5) adding sodium carbonate and sodium sulfate into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate and the sodium sulfate are respectively 5% and 5% of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and carrying out reduction roasting for 60min at 1000 ℃;
the obtained product is crushed and ground until the grain size is 85% at-0.074 mm, magnetic separation is carried out by adopting 800Gs magnetic field strength, the Co grade in the obtained magnetic product is 1.84%, the Co recovery rate is 75.87%, the Fe grade is 91.56%, and the Fe recovery rate is 79.12%.
Example 2:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
(1) the low-cobalt polymetallic sulphide ore with the Fe content of 36.17 percent and the Co content of 0.047 percent is crushed and ground until-200 meshes account for 85 percent;
(2) and carrying out sulphide ore flotation on the finely ground low-cobalt polymetallic sulphide ore, wherein the collecting agent is butyl xanthate, the inhibitor is sodium citrate, the regulator is sodium hydroxide, the activating agent is copper sulfate, the foaming agent is second oil, and the addition amounts are 150g/t, 75g/t, 800g/t, 70g/t and 50g/t respectively, so as to obtain cobalt sulphide concentrate with 41.08% of Fe and 0.23% of Co after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 10%, the roasting temperature is 900 ℃, and the roasting time is 120 min;
(4) and sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 1000Gs to obtain the cobalt-iron concentrate with the Fe content of 45.36 percent and the Co content of 1.52 percent.
(5) Adding sodium carbonate, sodium sulfate and sodium humate into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate, the sodium sulfate and the sodium humate are respectively 5%, 5% and 5% of the mass of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and reducing and roasting for 90min at 1100 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 90%, magnetic separation is carried out by adopting 1100Gs magnetic field strength, the Co grade in the obtained magnetic product is 5.32%, the recovery rate of Co is 68.87%, the Fe grade is 92.23%, and the recovery rate of Fe is 72.43%.
Example 3:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
(1) crushing and grinding low-cobalt polymetallic sulphide ore with Fe content of 38.94% and Co content of 0.023% to 90% with-200 meshes;
(2) and carrying out sulphide ore flotation on the finely ground low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl black, an inhibitor is sodium sulfite, a regulator is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil and the foaming agent are respectively 200g/t, 100g/t, 900g/t, 75g/t and 75g/t, and cobalt-sulfur concentrate with 42.78% of Fe and 0.18% of Co is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and then roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 10%, the roasting temperature is 800 ℃, and the roasting time is 120 min;
(4) and (3) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 1000Gs to obtain cobalt-iron concentrate with the Fe content of 46.56 percent and the Co content of 0.97 percent.
(5) Adding sodium carbonate, sodium sulfate and borax into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate, the sodium sulfate and the borax are respectively 5%, 5% and 5% of the mass of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and reducing and roasting for 90min at 1050 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 90 percent, magnetic separation is carried out by adopting 1100Gs magnetic field strength, the Co grade in the obtained magnetic product is 1.98 percent, the recovery rate of Co is 70.12 percent, the Fe grade is 94.53 percent, and the recovery rate of Fe is 72.45 percent.
Example 4:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
(1) the low-cobalt polymetallic sulphide ore with the Fe content of 38.94 percent and the Co content of 0.023 percent is crushed and ground until the grain size of-200 meshes accounts for 90 percent;
(2) and carrying out sulphide ore flotation on the finely ground low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl black, an inhibitor is sodium sulfite, an adjusting agent is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil, the foaming agent and the foaming agent are 250g/t, 150g/t, 1000g/t, 90g/t and 90g/t respectively, and cobalt-sulphur concentrate with the Fe content of 45.12% and the Co content of 0.20% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 15%, the roasting temperature is 950 ℃, and the roasting time is 30 min;
(4) and (3) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 1000Gs to obtain cobalt-iron concentrate with the Fe content of 47.33 percent and the Co content of 1.32 percent.
(5) Adding sodium carbonate and sodium humate into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate and the sodium humate are respectively 5% and 10% of the mass of the concentrate, uniformly mixing, agglomerating, adding anthracite as a reducing agent outside the agglomerate, and reducing and roasting for 90min at 1100 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 95%, magnetic separation is carried out by adopting 1100Gs magnetic field strength, the Co grade in the obtained magnetic product is 2.89%, the recovery rate of Co is 67.75%, the Fe grade is 96.33%, and the recovery rate of Fe is 70.51%.
Example 5:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
(1) low-cobalt polymetallic sulphide ore with Fe content of 28.34% and Co content of 0.013%, crushing and grinding to-200 meshes accounting for 95%;
(2) performing sulphide ore flotation on the finely ground low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, a regulator is sodium carbonate, an activating agent is copper sulfate, a foaming agent is turpentine, the adding amounts are respectively 250g/t, 150g/t, 1000g/t, 100g/t and 100g/t, and cobalt-sulfur concentrate with the Fe content of 30.89% and the Co content of 0.20% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 10%, the roasting temperature is 700 ℃, and the roasting time is 180 min;
(4) and sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs to obtain cobalt-iron concentrate with the Fe content of 38.85 percent and the Co content of 0.86 percent.
(5) Adding sodium carbonate, sodium humate and borax into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate, the sodium humate and the borax are respectively 5%, 10% and 5% of the mass of the concentrate, uniformly mixing, agglomerating, adding anthracite as a reducing agent into the agglomerates, and reducing and roasting for 120min at 1100 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 95 percent, magnetic separation is carried out by adopting 1100Gs magnetic field strength, the Co grade in the obtained magnetic product is 1.88 percent, the recovery rate of Co is 72.63 percent, the Fe grade is 90.56 percent, and the recovery rate of Fe is 76.89 percent.
Example 6:
the embodiment provides a method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores, which comprises the following steps:
(1) low-cobalt polymetallic sulphide ore with Fe content of 28.34% and Co content of 0.013%, crushing and grinding the low-cobalt polymetallic sulphide ore to-200 meshes accounting for 95%;
(2) and carrying out sulphide ore flotation on the finely ground low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, a regulator is soda ash, an activating agent is copper sulfate, a foaming agent is turpentine, the addition amounts of the turpentine are 200g/t, 100g/t, 850g/t, 70g/t and 90g/t respectively, and cobalt-sulfur concentrate with 37.56% of Fe and 0.19% of Co is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 15%, the roasting temperature is 900 ℃, and the roasting time is 60 min;
(4) and (3) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field strength of 800Gs to obtain cobalt-iron concentrate with the Fe content of 37.88% and the Co content of 0.82%.
(5) Adding sodium carbonate, sodium sulfate, sodium humate and borax into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate, the sodium sulfate, the sodium humate and the borax are respectively 5%, 10% and 5% of the mass of the concentrate, uniformly mixing, agglomerating, adding anthracite as a reducing agent into the agglomerates, and carrying out reduction roasting for 120min at 1100 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 95 percent, magnetic separation is carried out by adopting 1000Gs magnetic field strength, the Co grade in the obtained magnetic product is 1.64 percent, the recovery rate of Co is 79.45 percent, the Fe grade is 90.12 percent, and the recovery rate of Fe is 77.45 percent.
Comparative example 1
The comparative example provides a process for obtaining metallic cobalt by the conventional recovery and extraction of cobalt-containing pyrite. The specific process comprises the following steps: sulfating roasting-leaching-purifying extraction-cobalt precipitation process.
The process is adopted to recover the cobalt in the raw ore in the embodiment 1, and the specific steps are as follows:
(1) low-cobalt polymetallic sulphide ore with the Fe content of 36.17 percent and the Co content of 0.047 percent is crushed and ground until-200 meshes account for 85 percent;
(2) and after fine grinding, performing flotation on the sulphide ore in the low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, an adjusting agent is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil and the second oil are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt sulphur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) And adding 5 wt% of sodium sulfate into the cobalt-sulfur concentrate obtained by flotation, uniformly mixing, and roasting in a muffle furnace at 650 ℃ for 120 min.
(4) And (3) using 30g/L sulfuric acid as a leaching agent for the product after the vulcanization roasting, wherein the leaching temperature is 80 ℃, the leaching time is 3 hours, the solid-to-liquid ratio of the leaching solution is 3, the stirring speed is 300r/min, and the cobalt-containing concentrate with the cobalt grade of 0.19% is obtained, and the leaching rate of cobalt is 84.52%.
(6) Mixing 97.5% octanoic acid with 200g/L sodium carbonate, and using the mixture as an extractant to remove iron in cobalt-containing concentrate, wherein the extraction temperature is 15 ℃, the extraction phase and the phase separation are respectively carried out for 5min, the iron removal rate reaches 99.85%, and the cobalt content in the cobalt-containing solution after extraction is 0.68 g/L.
(7) Adding Na into the cobalt-containing solution 2 CO 3 Precipitating cobalt, wherein the pH value of the cobalt precipitation reaction is 9.2, the temperature is 70 ℃, the cobalt precipitation time is 90min, and then dissolving the obtained cobalt precipitation slag with concentrated sulfuric acid to obtain a cobalt-containing solution containing 6.5g/L of cobalt.
(8) And adding NaF into the obtained cobalt-containing solution to remove calcium and magnesium impurities, wherein the reaction temperature is 70 ℃, the pH value is 5.0, and the reaction time is 60min to obtain a solution containing cobalt of 6.3 g/L.
(9) Adding NaNO into the cobalt-containing solution with iron, calcium and magnesium impurities removed 3 -KCl mixed liquor, the dosage ratio of the two is 2.5: 1, the obtained cobalt-containing precipitate is potassium cobalt nitrite.
(10) Heating and decomposing potassium cobalt nitrite at 300 ℃ to obtain Co 2 O 3 Product, overall cobalt recovery at this point 43.25%.
From the steps, the process flow is long, the recovery rate of cobalt is relatively low, the types of reagents used in each stage are many, the consumption is high, the environment is easily polluted, and the like.
Comparative example 2
This comparative example recovers cobalt from the raw ore described in example 1, differing from example 1 in that the oxygen concentration of the oxygen calcination differs: the oxygen concentration was 99.9%.
The method comprises the following specific steps:
(1) low-cobalt polymetallic sulphide ore with the Fe content of 36.17 percent and the Co content of 0.047 percent is crushed and ground until-200 meshes account for 85 percent;
(2) performing flotation on the sulphide ore in the low-cobalt polymetallic sulphide ore after fine grinding, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, a regulator is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the adding amounts are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt-sulfur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and then carrying out oxidizing roasting to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 99.9%, the roasting temperature is 300 ℃, and the roasting time is 60 min;
(4) and (3) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs, and displaying that the cobalt-iron concentrate cannot be obtained by sorting.
The results show that the iron in the cobalt-sulphur concentrate is completely oxidised to Fe due to too high oxygen concentration 2 O 3 Since it has no magnetic properties, it is impossible to further separate and extract iron and cobalt by magnetic separation.
Comparative example 3
This comparative example recovers cobalt from the raw ore described in example 1, differing from example 1 in the temperature and time of oxygen calcination: the roasting temperature is 300 ℃, and the roasting time is 15 min.
The method comprises the following specific steps:
(1) low-cobalt polymetallic sulphide ore with the Fe content of 36.17 percent and the Co content of 0.047 percent is crushed and ground until-200 meshes account for 85 percent;
(2) and after fine grinding, carrying out flotation on pyrite in the low-cobalt polymetallic sulfide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, an adjusting agent is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil and the second oil are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt-sulfur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 5%, the roasting temperature is 300 ℃, and the roasting time is 15 min;
(4) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs to obtain cobalt-iron concentrate with the Fe content of 39.33% and the Co content of 0.16%;
(5) adding sodium carbonate and sodium sulfate into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate and the sodium sulfate are respectively 5% and 5% of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and carrying out reduction roasting for 60min at 1000 ℃;
the obtained product is crushed and ground until the grain size is-0.074 mm and accounts for 85%, magnetic separation is carried out by adopting the magnetic field strength of 800Gs, the Co grade in the obtained magnetic product is 0.091%, the recovery rate of cobalt is 5.11%, the Fe grade is 45.23%, and the recovery rate of Fe is 15.26%.
The results show that: the temperature and time of oxygen roasting are not properly selected, and the grade and recovery rate of Co in the obtained magnetic product are too low.
Comparative example 4
This comparative example recovers cobalt from the raw ore described in example 1, with the difference from example 1 that: the additive is non-alkali metal salt magnesium chloride. The method comprises the following specific steps:
(1) low-cobalt polymetallic sulphide ore with the Fe content of 36.17 percent and the Co content of 0.047 percent is crushed and ground until-200 meshes account for 85 percent;
(2) and after fine grinding, carrying out flotation on pyrite in the low-cobalt polymetallic sulphide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, a regulator is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the adding amounts are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt-sulfur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 5%, the roasting temperature is 400 ℃, and the roasting time is 20 min;
(4) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs to obtain cobalt-iron concentrate with the Fe content of 40.21 percent and the Co content of 0.81 percent;
(5) adding magnesium chloride into the cobalt-iron concentrate, wherein the addition amount of the magnesium chloride is 5% of that of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and reducing and roasting for 60min at 1000 ℃;
the obtained product is crushed and ground until the grain size is 85% at-0.074 mm, magnetic separation is carried out by adopting the magnetic field strength of 800Gs, the Co grade in the obtained magnetic product is 0.12%, the recovery rate of Co is 8.32%, the Fe grade is 45.64%, and the recovery rate of Fe is 10.25%.
The result shows that when the additive is not properly selected, the grade of cobalt and iron in the product obtained after solid reduction is reduced rather than that of cobalt-iron concentrate, and the recovery rate of cobalt and iron in the product is low.
Comparative example 5
This comparative example recovers cobalt from the raw ore described in example 1, with the difference from example 1: the reduction roasting temperature and time are different: reducing and roasting at 900 deg.c for 30 min. The method comprises the following specific steps:
(1) crushing and grinding low-cobalt polymetallic sulphide ore with the Fe content of 36.17% and the Co content of 0.047% to 85% with a grain size of-200 meshes;
(2) and after fine grinding, carrying out flotation on pyrite in the low-cobalt polymetallic sulfide ore, wherein a collecting agent is butyl xanthate, an inhibitor is sodium citrate, an adjusting agent is sodium hydroxide, an activating agent is copper sulfate, a foaming agent is second oil, the addition amounts of the second oil and the second oil are respectively 100g/t, 50g/t, 600g/t, 50g/t and 20g/t, and cobalt-sulfur concentrate with the Fe content of 30.22% and the Co content of 0.17% is obtained after flotation.
(3) Drying the cobalt-sulfur concentrate, and roasting with weak oxygen to obtain cobalt-containing iron oxide, wherein the oxygen concentration is 5%, the roasting temperature is 400 ℃, and the roasting time is 20 min;
(4) sorting the obtained cobalt-containing iron oxide by adopting the magnetic field intensity of 800Gs to obtain cobalt-iron concentrate with the Fe content of 40.21 percent and the Co content of 0.81 percent;
(5) adding sodium carbonate and sodium sulfate into the cobalt-iron concentrate, wherein the addition amounts of the sodium carbonate and the sodium sulfate are respectively 5% and 5% of the concentrate, uniformly mixing, agglomerating, adding lignite as a reducing agent into the agglomerates, and carrying out reduction roasting for 30min at 900 ℃;
the obtained product is crushed and ground until the grain size is 85% at-0.074 mm, magnetic separation is carried out by adopting the magnetic field strength of 800Gs, the Co grade in the obtained magnetic product is 0.85%, the recovery rate of Co is 20.56%, the Fe grade is 50.46%, and the recovery rate of Fe is 40.12%.
The result shows that when the reduction temperature and time are not properly selected, cobalt and iron in the cobalt-iron concentrate can not be well reduced, the grade of the cobalt and the grade of the iron in the reduced magnetic product are improved by a small extent compared with that of the cobalt-iron concentrate, and the recovery rate of the cobalt and the iron in the product is low.
Although the invention has been described in detail with respect to the general description and the specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A method for synchronously recovering cobalt and iron from low-cobalt multi-metal sulfide ores is characterized by comprising the following steps:
s1, pre-enriching by flotation to obtain cobalt-sulfur concentrate;
s2, drying the obtained cobalt-sulfur concentrate, and roasting with weak oxygen to obtain an oxide containing cobalt and iron;
s3, carrying out magnetic separation on the oxide containing cobalt and iron to obtain cobalt and iron concentrate, and then carrying out reduction roasting on the obtained cobalt and iron concentrate to obtain a cobalt and iron metal solid solution product.
2. The method for synchronously recycling the cobalt and the iron from the low-cobalt polymetallic sulphide ore according to claim 1, wherein in the step S2, the conditions of the weak oxygen roasting are as follows: the oxygen concentration is 5-25%, the roasting temperature is 600-1050 ℃, and the roasting time is 30-180 min.
3. The method for synchronously recycling the cobalt and the iron from the low-cobalt multi-metal sulfide ore according to claim 2, wherein the process of the step S3 is as follows:
(1) carrying out magnetic separation on the oxide containing cobalt and iron obtained in the step S2 to obtain cobalt and iron concentrate;
(2) adding an additive into the obtained cobalt-iron concentrate, uniformly mixing, agglomerating, and carrying out reduction roasting;
(3) and cooling the obtained reduction product, and then carrying out ore grinding-magnetic separation to obtain magnetic minerals, namely the cobalt-iron metal solid solution product.
4. The method for synchronously recovering the cobalt and the iron from the low-cobalt multi-metal sulphide ore according to the claim 3, characterized in that in the step (2), the additive is alkali metal salt;
the total addition amount of the alkali metal salt is 10-30% of the mass of the cobalt-iron concentrate;
preferably, the alkali metal salt is one or more of sodium carbonate, sodium sulfate, sodium humate or borax.
5. The method for synchronously recycling the cobalt and the iron from the low-cobalt multi-metal sulphide ore according to claim 4, wherein the reducing agent used for the reduction roasting is coal powder;
the reducing roasting conditions are as follows: the temperature is 1000-1100 ℃.
6. The method for synchronously recycling the cobalt and the iron from the low-cobalt polymetallic sulphide ore according to claim 5, wherein the magnetic separation conditions are as follows: the magnetic field intensity is 800Gs-2000 Gs;
preferably, the granularity of the mineral in the step (3) is controlled to be more than 80% at-0.074 mm before the magnetic separation is carried out.
7. The method for synchronously recovering the cobalt and the iron from the low-cobalt polymetallic sulphide ore according to claim 6, wherein in the step S1, the flotation agents adopted by the flotation comprise collectors, inhibitors, regulators, activators and frothers;
the collecting agent is xanthate and/or black powder;
the inhibitor is sulfite and/or citrate;
the regulator is one or more of caustic soda, lime, soda ash or sulfuric acid;
the activator is a metal sulfate;
the foaming agent is second oil and/or turpentine;
the addition amounts of the collecting agent, the inhibitor, the regulator, the activator and the foaming agent are respectively 50g/t-250g/t, 25g/t-150g/t, 600g/t-1000g/t, 25g/t-100g/t and 0g/t-100 g/t.
8. The method for synchronously recycling the cobalt and the iron from the low-cobalt multi-metal sulfide ore according to claim 7, wherein before the flotation, the raw ore is crushed and ground into-200 meshes which account for more than 80%.
9. The method for synchronously recovering the cobalt and the iron from the low-cobalt multi-metal sulphide ore according to any one of the claims 1 to 8, characterized in that the average content of the cobalt in the low-cobalt multi-metal sulphide ore is 0.02 percent.
10. The method for synchronously recovering cobalt and iron from low-cobalt polymetallic sulphide ores according to claim 1, characterized by comprising the following steps:
the first step is as follows: crushing and grinding the low-cobalt polymetallic sulphide ore raw ore until the crushed raw ore is-200 meshes and accounts for more than 80 percent, and uniformly mixing the crushed raw ore powder;
the second step is that: carrying out flotation on pyrite in low-cobalt polymetallic sulphide ore raw ore, wherein a target product obtained by the flotation is sulphide ore concentrate, and the main components of the sulphide ore concentrate are pyrite and pyrrhotite;
the flotation reagent comprises a collecting agent, an inhibitor, a regulator, an activator and a foaming agent, and the addition amounts are respectively 50g/t-250g/t, 25g/t-150g/t, 600g/t-1000g/t, 25g/t-100g/t and 0g/t-100 g/t;
the third step: drying the cobalt-sulfur concentrate obtained by flotation, and roasting the obtained dry cobalt-sulfur concentrate with weak oxygen to obtain a roasted product which is mainly cobalt-containing iron oxide;
wherein, the oxygen concentration is 5 to 25 percent, the roasting temperature is 600 to 1050 ℃, and the roasting time is 30 to 180 min;
the fourth step: carrying out magnetic separation on the cobalt-containing iron oxide obtained in the third step by adopting a magnetic field intensity of 800Gs-2000Gs to obtain cobalt-iron concentrate;
the fifth step: adding an additive into the cobalt-iron concentrate obtained in the fourth step, uniformly mixing, agglomerating, and carrying out reduction roasting; cooling the reduction product, crushing, grinding until the grain size is more than 80% at minus 0.074mm, and performing magnetic separation by adopting the magnetic field intensity of 800Gs-2000Gs to obtain the magnetic mineral which is a cobalt iron product;
wherein, the coal powder is used as a reducing agent and is reduced and roasted for 60min to 120min at the temperature of 1000 ℃ to 1100 ℃.
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