CN115725838A - Method for extracting valuable metal from ocean polymetallic nodule - Google Patents
Method for extracting valuable metal from ocean polymetallic nodule Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for extracting valuable metals from ocean polymetallic nodules, which comprises the following steps: sequentially crushing, finely grinding and drying the ocean polymetallic nodule to obtain ocean polymetallic nodule powder, placing the ocean polymetallic nodule powder in a reducing gas atmosphere, carrying out selective reduction at the temperature of 300-800 ℃, mixing the obtained reduced system with an inorganic acid solution, and leaching to obtain a leaching solution containing valuable metals. The method is carried out at the low temperature of 300-800 ℃, so that most of Mn (IV) in ocean polymetallic nodules is converted into Mn (II) or Mn (III), part of Fe (III) is converted into Fe (II), ni (II), co (II) and Cu (II) are not reduced, mn (II) or Mn (III) minerals which are easy to react with inorganic acid and valuable metals such as Ni (II), co (II), cu (II) and the like can be leached, the valuable metals do not need to be reduced into a metal state, the reduction temperature, the energy consumption and the cost are reduced, and the leaching rate of manganese, nickel, cobalt and copper is obviously improved.
Description
Technical Field
The invention relates to the field of extraction of valuable metals in oceans, in particular to a method for extracting valuable metals from oceans polymetallic nodules.
Background
Ocean polymetallic nodule is one very important strategic reserve resource, and is rich in manganese, iron and other valuable metals. Typical mineral phases of manganese in ocean polymetallic nodules are mainly birnessite, barium-magnesiate and delta-MnO 2 And the like, iron is closely intercalated with manganese, and goethite or amorphous iron is common. Valuable metals such as nickel, cobalt, copper, etc. are present in the iron-manganese mineral phase in an adsorbed state or in the same phase as the iron-manganese mineral phase. Because nickel, cobalt and copper in the polymetallic nodule do not exist in an independent mineral form, physical mineral separation is difficult to enrich, and smelting processing treatment is required to be directly carried out.
The oceanic polymetallic nodule smelting and processing research begins in the 60's of the 20 th century, and there are dozens of schemes proposed by countries in the world, including smelting-leaching method and wet reduction-leaching method, but the methods are not suitable for industrial application in research and development stages. The smelting-leaching method needs to prepare the main components firstlyThe method is divided into iron-nickel-cobalt-copper alloy or sulfide is further added to convert the iron-nickel-cobalt-copper alloy into sulfonium (metal sulfide mutual solution), and then the alloy or the sulfonium is subjected to oxidation leaching to recover valuable metals such as nickel, cobalt and copper in the alloy or the sulfonium. The disadvantages of the smelting-leaching method are that: 1) The smelting needs high temperature of about 1400 ℃, and the energy consumption is high; 2) The grades of nickel, cobalt and copper in the alloy or matte obtained by smelting are still not high, the alloy or matte cannot be directly applied, and the valuable metals of nickel, cobalt and copper can be efficiently recovered only by wet treatment; 3) The smelting-leaching method can not directly obtain manganese products, but produces manganese-rich slag which can be specially treated to prepare manganese alloy, when manganese content in ocean polymetallic nodule<When the content is 20%, the preparation of manganese alloy is difficult to satisfy. Because manganese in the ocean polymetallic nodule mainly exists in the form of tetravalent manganese, manganese (IV) needs to be reduced to a low valence state during wet extraction so as to leach valuable metals such as nickel, cobalt, copper and the like embedded in manganese minerals. The wet reduction-leaching method mainly comprises two types of wet reduction-sulfuric acid leaching and wet reduction-ammonia leaching. The research is most common by adopting wet reduction-sulfuric acid leaching, and the reducing agent is pyrite (FeS) 2 ) Sulfurous acid and salts (e.g. H) 2 SO 3 、SO 2 、Na 2 SO 3 Etc.), ferrous salt, organic matter (such as starch), etc., the method can obtain higher leaching rate of nickel, cobalt, manganese and copper, but the price of the reducing agent (such as starch and SO) is high 2 ) Or other impurity elements (such as pyrite and ferrous salt) are introduced, so that the extraction cost is high or the generation amount of waste residues is increased. The wet reduction-ammonia leaching process can preferentially leach copper, nickel and cobalt in the raw materials, has good leaching selectivity and is easier for subsequent separation. However, compared with the wet reduction-acid leaching method, the leaching rate of nickel, cobalt and copper is low, particularly the leaching rate of cobalt is low, manganese still remains in the leaching residue in the process, and the wet extraction of manganese cannot be realized.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for extracting valuable metals from ocean polymetallic nodules, which aims to solve the problems of high energy consumption, high cost and low leaching rate of valuable metals in the existing method for extracting valuable metals from ocean polymetallic nodules.
The technical scheme of the invention is as follows:
a method for extracting valuable metals from ocean polymetallic nodules, which comprises the following steps:
providing an ocean polymetallic nodule;
sequentially crushing, finely grinding and drying the ocean polymetallic nodule to obtain ocean polymetallic nodule powder;
placing the oceanic polymetallic nodule powder in a reducing gas atmosphere, and performing selective reduction at the temperature of 300-800 ℃ to obtain a reduced system;
and mixing the reduced system with an inorganic acid solution, and leaching to obtain a leaching solution containing valuable metals.
Optionally, the reducing gas is selected from one of carbon monoxide, natural gas, coal gas and hydrogen.
Optionally, the ocean polymetallic nodule powder has a particle size of 30 mesh or less, and/or the ocean polymetallic nodule powder has a moisture content of less than 2%.
Optionally, the oceanic polymetallic nodule powder is placed in a reduction furnace, and is introduced with reducing gas, and is subjected to selective reduction at the temperature of 500-600 ℃ to obtain a reduced system.
Optionally, the selective reduction time is 0.5-4h.
Optionally, H in the inorganic acid solution + The concentration of (B) is 1.0-10.0 mol/L.
Optionally, the inorganic acid in the inorganic acid solution is selected from one or more of sulfuric acid, hydrochloric acid and nitric acid.
Optionally, in the step of mixing the reduced system with an inorganic acid solution for leaching, the ratio of the reduced system to the inorganic acid solution is 1g: (2-10) mL.
Optionally, the leaching temperature is 20-200 ℃, and/or the leaching time is 0.5-10 h.
Optionally, the reduced system is mixed with an inorganic acid solution for leaching, and after solid-liquid separation, a leachate containing valuable metals is obtained.
Has the beneficial effects that: the invention provides a method for extracting valuable metals from ocean polymetallic nodules, which comprises the steps of crushing and finely grinding the ocean polymetallic nodules, and carrying out selective reduction at the low temperature of 300-800 ℃, so that most Mn (IV) in the ocean polymetallic nodules is converted into Mn (II) or Mn (III), part Fe (III) is converted into Fe (II), and Ni (II), co (II) and Cu (II) are not reduced; the selective reduction not only converts Mn (IV) mineral which is difficult to react with inorganic acid into Mn (II) or Mn (III) mineral which is easy to react with the inorganic acid, but also can release valuable metals such as Ni (II), co (II), cu (II) and the like which exist in the iron-manganese ore phase in a mode of adsorption state or homogeneous phase of the like when the Mn (II) or Mn (III) is leached by the inorganic acid, thereby obviously improving the leaching rate of nickel, cobalt and copper.
Compared with the smelting-leaching method, the method for extracting valuable metals from ocean polymetallic nodules provided by the invention does not need to reduce the valuable metals into a metallic state, obviously reduces the reduction temperature, simultaneously can realize the simultaneous leaching of manganese, nickel, cobalt and copper, and is beneficial to the wet recovery of the valuable metals such as manganese, nickel, cobalt and copper. The method provided by the invention effectively solves the problems that the smelting-leaching method is high in reduction temperature and energy consumption and cannot directly obtain a manganese product.
Compared with the wet reduction-leaching method, the method for extracting valuable metals from ocean polymetallic nodules provided by the invention has the advantages that the leaching rate of the valuable metals of nickel, cobalt and copper is high, the adopted gas reducing agent is cheap and easy to obtain, and other impurities are not introduced in the reduction process, so that the extraction cost is reduced, and the generation amount of waste residues is reduced. The method provided by the invention can effectively solve the problems of high cost, large slag amount and low leaching rate of valuable metals in a wet reduction-leaching method.
Drawings
FIG. 1 is a process flow diagram of the extraction of valuable metals from ocean polymetallic nodules in the example of the present invention.
FIG. 2 is an XRD pattern of an ocean polymetallic nodule used in examples 1-8 of the present invention.
FIG. 3 is an XRD pattern of the reduced system in example 2 of the present invention.
Detailed Description
The present invention provides a method for extracting valuable metals from ocean polymetallic nodules, and the present invention is further described in detail below to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Typical mineral phases of manganese in the ocean polymetallic nodules are mainly birnessite, barium-magnesiate and delta-MnO 2 And the like, iron is closely intercalated with manganese, and goethite or amorphous iron is common. The valuable metals such as nickel, cobalt, copper, etc. are present in the iron-manganese ore phase in an adsorbed state or in the same phase as the species. Because nickel, cobalt and copper in the polymetallic nodule do not exist in an independent mineral form, physical mineral separation is difficult to enrich, and smelting processing treatment needs to be directly carried out, but the main smelting processing treatment methods, namely a smelting-leaching method and a wet reduction-leaching method, have various defects and shortcomings, such as high temperature, high energy consumption, high cost, low leaching rate of valuable metals, incapability of directly obtaining manganese products and the like. Based on this, the embodiment of the present invention provides a method for extracting valuable metals from ocean polymetallic nodules, as shown in fig. 1, wherein the method comprises the following steps:
s11, providing oceanic polymetallic nodules;
s12, sequentially crushing, finely grinding and drying the ocean polymetallic nodule to obtain ocean polymetallic nodule powder;
s13, placing the oceanic polymetallic nodule powder in a reducing gas atmosphere, and carrying out selective reduction at the temperature of 300-800 ℃ to obtain a reduced system;
s14, mixing the reduced system with an inorganic acid solution, and leaching to obtain a leaching solution containing valuable metals.
In the embodiment, ocean polymetallic nodules are sequentially subjected to pretreatment processes such as crushing, fine grinding and drying to obtain ocean polymetallic nodule powder, the ocean polymetallic nodule powder reacts with reducing gas at a low temperature of 300-800 ℃ to perform selective reduction, so that most Mn (IV) in the ocean polymetallic nodules is converted into Mn (II) or Mn (III), part Fe (III) is converted into Fe (II), ni (II), co (II) and Cu (II) are not reduced, and then the ocean polymetallic nodule powder is mixed with inorganic acid to perform leaching of valuable metals, so that the valuable metals such as nickel, cobalt, copper, manganese and the like are transferred into a solution from a solid phase, and efficient extraction of the valuable metals such as nickel, cobalt, manganese and the like in the ocean polymetallic nodules is realized. The selective reduction not only converts Mn (IV) mineral which is difficult to react with inorganic acid into Mn (II) or Mn (III) mineral which is easy to react with the inorganic acid, but also can release valuable metals such as Ni (II), co (II), cu (II) and the like which are in an adsorption state or in a homogeneous phase manner in the process of leaching Mn (II) or Mn (III) by using the inorganic acid, thereby further remarkably improving the leaching rate of nickel, cobalt and copper, and the leaching rate of each valuable metal in the embodiment can reach more than 95%.
Note that, in the parentheses after Mn, fe, ni, co, and Cu, roman numerals IV, III, and II represent valency, IV represents +4, III represents +3, and II represents +2, that is, mn (IV) and Mn (II) represent + 4-valent Mn and + 2-valent Mn, respectively, fe (III) and Fe (II) represent + 3-valent Fe and + 2-valent Fe, respectively, and Ni (II), co (II), and Cu (II) represent + 2-valent Ni, co, and Cu, respectively.
Compared with the smelting-leaching method, the method for extracting valuable metals from ocean polymetallic nodules provided by the embodiment does not need to reduce the valuable metals into a metallic state, obviously reduces the reduction temperature, simultaneously can realize the simultaneous leaching of manganese, nickel, cobalt and copper, and is beneficial to the wet recovery of the valuable metals such as manganese, nickel, cobalt and copper. The method provided by the embodiment effectively solves the problems that the smelting-leaching method is high in reduction temperature and high in energy consumption and cannot directly obtain a manganese product.
Compared with a wet reduction-leaching method, the method for extracting valuable metals from oceanic polymetallic nodules provided by the embodiment has the advantages that the leaching rate of the valuable metals of nickel, cobalt and copper is high, the adopted gas reducing agent is cheap and easy to obtain, other impurities cannot be introduced in the reduction process, the extraction cost is reduced, and the generation amount of waste residues is reduced. The method provided by the embodiment can effectively solve the problems of high cost, large slag amount and low leaching rate of valuable metals in a wet reduction-leaching method.
In step S11, the oceanic polymetallic nodules contain valuable metals such as manganese, iron, nickel, cobalt, copper and the like, wherein typical mineral phases of the manganese mainly comprise birnessite, barium-magnesiolite and delta-MnO 2 And the like, iron and manganese are closely embedded and symbiotic, and valuable metals such as nickel, cobalt, copper and the like exist in the mineral phase of iron and manganese in an adsorption state or in the same-class phase mode, wherein manganese is mainly in a valence of +4, iron is mainly in a valence of +3, and nickel, cobalt and copper are mainly in a valence of + 2. While +4 valent manganese cannot be leached directly and needs to be reduced to a lower valence state.
In step S12, in one embodiment, the ocean polymetallic nodule powder has a particle size of 30 mesh or less. The smaller the particle size, the larger the specific surface area, the more easily and thoroughly the reduction reaction with the reducing gas is performed under the same conditions, and the particle size of the ocean polymetallic nodule powder should be 30 mesh or smaller in order to allow the ocean polymetallic nodule powder to selectively reduce with the reducing gas.
In one embodiment, the ocean polymetallic nodule powder has a particle size of 60 mesh or less.
In a specific embodiment, the particle size of the oceanic polymetal bonding powder is 100 mesh.
In one embodiment, the oceanic polymetallic nodule powder has a moisture content of less than 2%. That is, the mass of water in the ocean polymetallic nodule powder is less than 2% of the mass of the ocean polymetallic nodule powder. The control of the water content is beneficial to the subsequent selective reduction reaction.
In one embodiment, the water content of the oceanic polymetallic nodule powder is less than 0.5%, and in order to further reduce the effect of moisture, the water content of the oceanic polymetallic nodule powder should be controlled below 0.5%.
In step S13, the ocean polymetallic nodule powder and the reducing gas are selectively reduced at a low temperature of 300-800 ℃, so that most of Mn (IV) in the ocean polymetallic nodule is converted into Mn (II) or Mn (III), part of Fe (III) is converted into Fe (II), and Ni (II), co (II) and Cu (II) keep the original valence state and are not reduced, that is, the obtained reduced system comprises Mn (II), mn (III), fe (II), ni (II), co (II), cu (II) and other valuable metals, wherein the Mn (II) or Mn (III) mineral is easy to react with an inorganic acid for leaching, and in step S14, when Mn (II) or Mn (III) is leached by the inorganic acid, ni (II), co (II), cu (II) and other valuable metals which are present in the iron manganese ore phase in an adsorption state or in a similar manner can be released, so that the leaching rate of nickel, cobalt and copper is significantly improved.
In step S13, in an embodiment, the reducing gas is selected from one of carbon monoxide, natural gas, coal gas, and hydrogen, but is not limited thereto. The reducing gas in this example is inexpensive and readily available. Compared with a wet reduction-sulfuric acid leaching method (the adopted reducing agent is high in price or other impurity elements can be introduced), the method has the advantages that the reducing gas is low in price and easy to obtain, the cost can be reduced, in addition, the reduced system only contains original element components of the oceanic polymetallic nodule, other impurity elements are not introduced, and the extraction cost and the generation amount of waste residues can be reduced.
In one embodiment, the oceanic polymetallic nodule powder is placed in a reduction furnace and introduced with reducing gas for selective reduction at the temperature of 500-600 ℃ to obtain a reduced system. In this embodiment, the reducing gas may be continuously introduced into the reduction furnace or intermittently introduced into the reduction furnace.
In one embodiment, the reduction furnace is selected from one of a tube furnace, a shaft furnace, a rotary kiln, but is not limited thereto.
In one embodiment, the selective reduction is for a time of 0.5 to 4 hours. The selective reduction time also affects the degree of reduction reaction, and the selective reduction time is controlled to be 0.5-4h, so that the ocean polymetallic nodule powder and the reducing gas are subjected to selective reduction, namely, mn (IV) and Fe (III) are reduced, and Ni (II), co (II) and Cu (II) are not reduced.
In a more specific embodiment, the selective reduction is for a time of 1 to 3 hours.
In step S14, inIn one embodiment, the inorganic acid solution has H + The concentration of (b) is 1.0-10.0 mol/L. This concentration allows maximum leaching of nickel, cobalt, copper and manganese.
In a more specific embodiment, the inorganic acid solution is H + The concentration of (b) is 2.0-7.0 mol/L.
In one embodiment, the inorganic acid in the inorganic acid solution is selected from one or more of sulfuric acid, hydrochloric acid, and nitric acid, but is not limited thereto.
In one embodiment, in the step of mixing the reduced system with an inorganic acid solution for leaching, the ratio of the reduced system to the inorganic acid solution is 1g: (2-10) mL. The proportion can ensure that nickel, cobalt, copper and manganese are leached to the maximum extent
In a more specific embodiment, in the step of mixing the reduced system with an inorganic acid solution for leaching, the ratio of the reduced system to the inorganic acid solution is 1g: (3-6) mL.
In one embodiment, the temperature of the leaching is 20 to 200 ℃.
In one embodiment, the leaching time is 0.5 to 10 hours.
In one embodiment, the temperature of the leaching is 20-200 ℃, and the time of the leaching is 0.5-10 h. According to the leaching rate of each metal, the leaching temperature and time are set, when the leaching temperature is 20-200 ℃, the time is 0.5-10 h, the optimal leaching rate can be obtained, and the leaching rate of each metal can reach more than 95%.
In a more specific embodiment, the temperature of the leaching is 60-160 ℃ and the time is 1-4 h.
In one embodiment, the reduced system is mixed with an inorganic acid solution to perform leaching, and after solid-liquid separation, a leaching solution containing valuable metals and a leaching residue are obtained. In the present embodiment, solid-liquid separation is performed by a method including, but not limited to, filtration.
The invention is further illustrated by the following specific examples.
The same oceanic polymetallic nodules, whose main metal components are shown in table 1, were used in examples 1-8.
TABLE 1 major Metal component of oceanic polymetallic nodules
| Element(s) | Al | Fe | Mn | Ni | Co | Cu |
| Content% | 3.85 | 17.6 | 18.5 | 0.365 | 0.425 | 0.263 |
The ocean polymetallic nodules used in examples 1-8 were subjected to XRD test and their XRD patterns are shown in FIG. 2. From FIG. 2, it can be seen that manganese in the ocean polymetallic nodules exists mainly in the form of birnessite, the valence of Mn in the birnessite is +4, while nickel, cobalt and copper have no fixed phases and exist in the iron-manganese ore phase in an adsorbed state or in a homogeneous phase.
In examples 1 to 8, the leaching rate of each metal was calculated from the mass of the oceanic polymetallic nodule leaching material and the leaching residue and the percentage content of each metal therein, and the leaching rate E was calculated according to the formula (1):
E＝(M material ×C Material -M Slag ×C Slag )/(M Material ×C Material )×100％ (1)
In the formula (1), M Material 、M Slag Respectively representing the mass (g) and C of the oceanic polymetallic nodule leaching raw material and the leaching residue Material 、C Slag Respectively represents the mass percentage (%) of each metal in the oceanic polymetallic nodule leaching raw material and leaching slag, C Material 、C Slag Measured by chemical analysis.
Example 1
Crushing oceanic polymetallic nodule, fine grinding to 100 mesh, and drying to water content<0.5 percent to obtain oceanic polymetallic nodule powder. Respectively taking 100g of the oceanic polymetallic nodule powder and respectively adding the oceanic polymetallic nodule powder into 300mL of sulfuric acid solution (H) + Concentration 6.5 mol/L), and leaching under stirring at 60 deg.C (normal pressure) and 160 deg.C (pressure and pressure, about 0.8 MPa) for 1h. The leaching rates of nickel, cobalt, copper and manganese are shown in Table 2. As can be seen from table 2, when the oceanic polymetallic nodules are directly leached, the leaching rates of manganese are below 5% both in normal pressure leaching (60 ℃) and pressure leaching (160 ℃), and the leaching rates of cobalt, nickel and copper embedded in the crystal lattices of the sodium manganite are low due to the very low leaching rate of manganese, the leaching rates of cobalt, nickel and copper in normal pressure leaching (60 ℃) are respectively 11.2%, 37.8% and 76.5%, and the leaching rates of cobalt, nickel and copper in pressure leaching (160 ℃) are respectively 15.2%, 40.2% and 73.2%. Example 1 illustrates that the valuable metals cobalt, nickel, copper and manganese in the ocean polymetallic nodule are difficult to leach efficiently by direct leaching without reduction.
TABLE 2 leaching rate (%)
| The leaching temperature is lower | Ni | | Cu | Mn | |
| 60 | 37.8 | 11.2 | 76.5 | 2.34 | |
| 160 | 40.2 | 15.2 | 73.2 | 3.12 |
Example 2
Crushing the ocean polymetallic nodule in advance, finely grinding to 100 meshes, and drying until the water content is less than 0.5% to obtain ocean polymetallic nodule powder.
Placing oceanic polymetallic nodule powder in a tubular furnace, reducing for 2 hours at the temperature of 600 ℃ by adopting CO gas as a reducing agent, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system. The XRD pattern of the reduced system is shown in FIG. 3, and it can be seen from FIG. 3 that Fe and Mn in the reduced system both have independent mineral phases, namely Fe 3 O 4 And Mn 3 O 4 . It is shown that after reduction, most of Mn (IV) in the ocean polymetallic nodules has been converted to Mn (II) or Mn (III), while part of Fe (III) is converted to Fe (II).
100g of the above reduced system was added to 300mL of sulfuric acid solution (H) + Concentration of 6.5 mol/L), leaching for 1h at the temperature of 60 ℃ with stirring. The leaching rates of nickel, cobalt, copper and manganese are shown in Table 3. Compared with the embodiment 1, compared with direct leaching (no reduction process), the leaching rate of valuable metals of nickel, cobalt, copper and manganese is obviously improved by leaching oceanic polymetallic nodules after CO reduction. The leaching rates of the valuable metals of nickel, cobalt, manganese and copper are all more than 95 percent and are obviously higher than that of the unreduced valuable metals (example 1).
The leaching rate of nickel, cobalt, copper and manganese reaches more than 95 percent, which not only indicates that most of Mn (IV) in the ocean polymetallic nodule is reduced into Mn (II) or Mn (III), but also indicates that Ni (II), co (II) and Cu (II) are not reduced and maintain the original valence state.
TABLE 3 leaching rate of sulfuric acid leaching of system to each valuable metal after reduction of oceanic polymetal nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching rate (%) | 98.12 | 98.76 | 96.24 | 97.87 |
Example 3
Crushing ocean polymetallic nodule, grinding to 60 mesh, and drying to water content less than 1.5% to obtain ocean polymetallic nodule powder.
And (3) placing the oceanic polymetallic nodule powder into a rotary furnace, reducing for 0.5h at the temperature of 800 ℃ by adopting CO gas as a reducing agent, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
100g of the above reduced system was added to 500mL of hydrochloric acid solution (H) + Concentration of 4.0 mol/L), leaching at a temperature of 20 ℃ for 10h with stirring. The leaching rates of nickel, cobalt, copper and manganese are shown in Table 4, and the leaching rates of nickel, cobalt, copper and manganese are 93.12%, 95.36%, 86.24% and 96.87%, respectively.
TABLE 4 leaching rate of hydrochloric acid leaching of system after reduction of oceanic polymetal nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching Rate (%) | 93.12 | 95.36 | 86.24 | 96.87 |
Example 4
Crushing ocean polymetallic nodule in advance, fine grinding to 30 mesh, and drying to water content of less than 1.0% to obtain ocean polymetallic nodule powder.
And (3) placing the oceanic polymetallic nodule powder into a rotary furnace, reducing for 4 hours at the temperature of 300 ℃ by adopting CO gas as a reducing agent, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
100g of the above reduced system was added to 500mL of nitric acid solution (H) + Concentration of 4.0 mol/L), leaching at 100 ℃ for 0.5h with stirring. The leaching rates of nickel, cobalt, copper and manganese are shown in table 5, and the leaching rates of nickel, cobalt, copper and manganese are 96.12%, 94.54%, 92.13% and 97.37%, respectively.
TABLE 5 leaching rate of nitric acid leaching of system after reduction of oceanic polymetal nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching Rate (%) | 96.12 | 94.54 | 92.13 | 97.37 |
Example 5
Crushing the ocean polymetallic nodule in advance, finely grinding to 100 meshes, and drying until the water content is less than 0.5% to obtain ocean polymetallic nodule powder.
And (2) placing oceanic polymetallic nodule powder in a rotary furnace, reducing for 3 hours at the temperature of 500 ℃ by adopting CO gas as a reducing agent, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
1000g of the above reduced system was added to 2000mL of sulfuric acid solution (H) + Concentration of 10.0 mol/L), leaching for 1h at the temperature of 80 ℃ by stirring. The leaching rates of nickel, cobalt, copper and manganese are shown in table 6, and the leaching rates of nickel, cobalt, copper and manganese are 94.32%, 94.55%, 92.21% and 95.27%, respectively.
TABLE 6 leaching rate of sulfuric acid leaching of system after reduction of ocean polymetallic nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching rate (%) | 94.32 | 94.55 | 92.21 | 95.27 |
Example 6
Crushing ocean polymetallic nodule, grinding to 60 mesh, and drying to water content less than 0.5% to obtain ocean polymetallic nodule powder.
Placing oceanic polymetallic nodule powder in a rotary furnace, adopting coal gas as a reducing agent, reducing for 2 hours at the temperature of 500 ℃, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
100g of the above reduced system was added to 500mL of sulfuric acid solution (H) + Concentration 2.5 mol/L) and stirred at a temperature of 160 ℃ for 4h. The leaching rates of nickel, cobalt, copper and manganese are shown in table 7, and the leaching rates of nickel, cobalt, copper and manganese are respectively 98.36%, 98.78%, 96.09% and 98.11%.
TABLE 7 leaching rate of sulfuric acid leaching each valuable metal of the system after reduction of ocean polymetallic nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching Rate (%) | 98.36 | 98.78 | 96.09 | 98.11 |
Example 7
Crushing the ocean polymetallic nodule in advance, finely grinding to 60 meshes, and drying until the water content is less than 0.5% to obtain ocean polymetallic nodule powder.
Placing oceanic polymetallic nodule powder in a rotary furnace, reducing for 1h at the temperature of 600 ℃ by adopting hydrogen as a reducing agent, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
100g of the above reduced system was added to 1000mL of sulfuric acid solution (H) + Concentration 1.2 mol/L) and stirred at a temperature of 200 ℃ for 4h in an autoclave. The leaching rates of nickel, cobalt, copper and manganese are shown in Table 8, and the leaching rates of nickel, cobalt, copper and manganese are respectively 98.56%, 98.78%, 95.67% and 97.62%.
TABLE 8 leaching rate of sulfuric acid leaching of system after reduction of ocean polymetallic nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching rate (%) | 98.56 | 98.78 | 95.67 | 97.62 |
Example 8
Crushing the ocean polymetallic nodule in advance, finely grinding to 60 meshes, and drying until the water content is less than 0.5% to obtain ocean polymetallic nodule powder.
Placing oceanic polymetallic nodule powder in a shaft furnace, adopting coal gas as a reducing agent, reducing for 2 hours at the temperature of 600 ℃, and naturally cooling to room temperature after the reduction is finished to obtain a reduced system.
100g of the above reduced system was added to 600mL of sulfuric acid solution (H) + Concentration 2.0 mol/L) and stirred at a temperature of 140 ℃ for 4h in an autoclave. The leaching rates of nickel, cobalt, copper and manganese are shown in Table 9, and the leaching rates of nickel, cobalt, copper and manganese are 98.21%, 98.61%, 95.89% and 97.91%, respectively
TABLE 9 leaching rate of sulfuric acid leaching of system after reduction of ocean polymetallic nodule
| Element(s) | Ni | Co | Cu | Mn |
| Leaching Rate (%) | 98.21 | 98.61 | 95.89 | 97.91 |
In conclusion, the invention provides a method for extracting valuable metals from ocean polymetallic nodules, which comprises the steps of crushing and finely grinding the ocean polymetallic nodules, and performing selective reduction with reducing gas at the low temperature of 300-800 ℃, so that most Mn (IV) in the ocean polymetallic nodules is converted into Mn (II) or Mn (III), part Fe (III) is converted into Fe (II), and Ni (II), co (II) and Cu (II) are not reduced; the selective reduction not only converts Mn (IV) mineral which is hard to react with inorganic acid into Mn (II) or Mn (III) mineral which is easy to react with the inorganic acid, but also can release valuable metals such as Ni (II), co (II), cu (II) and the like which exist in the ferromanganese ore phase in a mode of adsorption state or homogeneous phase when the Mn (II) or Mn (III) is leached by the inorganic acid, thereby obviously improving the leaching rate of nickel, cobalt and copper.
Compared with the smelting-leaching method, the method for extracting valuable metals from ocean polymetallic nodules provided by the invention does not need to reduce the valuable metals into a metallic state, obviously reduces the reduction temperature, simultaneously can realize the simultaneous leaching of manganese, nickel, cobalt and copper, and is beneficial to the wet recovery of the valuable metals such as manganese, nickel, cobalt and copper. The method provided by the invention effectively solves the problems that the smelting-leaching method is high in reduction temperature and energy consumption and cannot directly obtain a manganese product.
Compared with the wet reduction-leaching method, the method for extracting valuable metals from ocean polymetallic nodules provided by the invention has the advantages that the leaching rate of the valuable metals of nickel, cobalt and copper is high, the adopted gas reducing agent is cheap and easy to obtain, and other impurities are not introduced in the reduction process, so that the extraction cost is reduced, and the generation amount of waste residues is reduced. The method provided by the invention can effectively solve the problems of high cost, large slag amount and low leaching rate of valuable metals in a wet reduction-leaching method.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for extracting valuable metals from ocean polymetallic nodules, comprising the steps of:
providing an ocean polymetallic nodule;
sequentially crushing, fine grinding and drying the ocean polymetallic nodule to obtain ocean polymetallic nodule powder;
placing the oceanic polymetallic nodule powder in a reducing gas atmosphere, and carrying out selective reduction at the temperature of 300-800 ℃ to obtain a reduced system;
and mixing the reduced system with an inorganic acid solution, and leaching to obtain a leaching solution containing valuable metals.
2. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said reducing gas is selected from one of carbon monoxide, natural gas, coal gas, hydrogen.
3. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said ocean polymetallic nodule powder has a particle size of 30 mesh or less and/or a water content of less than 2%.
4. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said ocean polymetallic nodule powder is placed in a reduction furnace and is introduced with reducing gas, and is subjected to selective reduction at 500-600 ℃ to obtain a reduced system.
5. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said selective reduction time is 0.5-4h.
6. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said inorganic acid solution contains H + The concentration of (B) is 1.0-10.0 mol/L.
7. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said inorganic acid in said inorganic acid solution is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid.
8. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein in said step of mixing said reduced system with a mineral acid solution and leaching, the ratio of said reduced system to said mineral acid solution is 1g: (2-10) mL.
9. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein the temperature of said leaching is 20-200 ℃ and/or the time of said leaching is 0.5-10 h.
10. The method for extracting valuable metals from ocean polymetallic nodules according to claim 1, wherein said reduced system is mixed with inorganic acid solution for leaching, and after solid-liquid separation, leachate containing valuable metals is obtained.
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| US4043806A (en) * | 1974-10-15 | 1977-08-23 | Kennecott Copper Corporation | Alloys from manganese nodules |
| CN1172167A (en) * | 1996-07-25 | 1998-02-04 | 冶金工业部长沙矿冶研究院 | Smelting-rusting-extraction method for extracting valuable metals from ocean polymetallic nodule |
| CN101701297A (en) * | 2009-11-19 | 2010-05-05 | 长沙矿冶研究院 | Ore blending and smelting method for ocean cobalt-rich crusts |
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| CN111876586A (en) * | 2020-07-29 | 2020-11-03 | 北京科技大学 | Method for comprehensively recovering all elements by roasting and reducing ocean cobalt-rich crusts through biomass |
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| US4043806A (en) * | 1974-10-15 | 1977-08-23 | Kennecott Copper Corporation | Alloys from manganese nodules |
| CN1172167A (en) * | 1996-07-25 | 1998-02-04 | 冶金工业部长沙矿冶研究院 | Smelting-rusting-extraction method for extracting valuable metals from ocean polymetallic nodule |
| CN101701297A (en) * | 2009-11-19 | 2010-05-05 | 长沙矿冶研究院 | Ore blending and smelting method for ocean cobalt-rich crusts |
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