A method for resource utilization of a submarine cobalt-manganese oxide ore wet metallurgy slag

Abstract

The application provides a method for recycling seabed cobalt-manganese oxide ore hydrometallurgy slag, and relates to the field of metallurgical industry. The method comprises the following steps: providing seabed cobalt-manganese oxide ore hydrometallurgy slag; mixing, reacting the seabed cobalt-manganese oxide ore hydrometallurgy slag, carbon monoxide and chlorine gas to obtain reaction slag, and collecting flue gas in the reaction process; condensing and crystallizing the flue gas to obtain iron chloride; washing the reaction slag by using an ether compound, and performing solid-liquid separation to obtain washing slag; performing water immersion and solid-liquid separation on the washing slag to obtain a manganese chloride solution. The iron and manganese extraction rate of the method is greater than 95%, the products formed by iron and manganese are different in boiling point and vapor pressure, and the products are separated step by step by controlling the reaction conditions, so that the problem that the products cannot be separated does not exist; the product collection process is simple, the iron product can be quickly collected by flue gas condensation, the reaction slag is washed to retain manganese chloride, and the product can be collected by dissolution and evaporation crystallization.

Description

Technical Field

[0001] This application relates to the metallurgical industry, and more particularly to a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore. Background Technology

[0002] Deep-sea mineral resources contain abundant valuable metals such as nickel, cobalt, copper, iron, and manganese, making them essential for metal smelting. Among the smelting technologies for deep-sea mineral resource development, sulfuric acid pressure leaching is a promising approach. By treating polymetallic oxide minerals through pressure leaching, valuable metals such as nickel, cobalt, and copper can be selectively extracted, while iron and manganese remain in the leaching residue. Hydrometallurgical slag mainly consists of oxides or hydrated oxides, and the residual iron and manganese within it have recovery value, although their content is much lower than that of conventional iron and manganese resources. How to extract and recover iron and manganese from this type of resource is a technical problem that needs to be solved for the further development of deep-sea resources.

[0003] For the treatment of secondary resources of smelting slag mainly composed of iron and manganese oxides, patent document CN118142543A discloses a method for leaching iron and manganese slag using titanium dioxide waste acid. The titanium dioxide waste acid can dissociate elements such as Fe, Mn, and Mg from the iron and manganese slag, and Ca is converted to CaSO4 and separated from the system. The Fe and Mn-containing solution is precipitated with ammonia water to obtain a composite oxide containing Mn and Fe, which can be used to prepare a denitrification catalyst after binding, drying, and calcination. However, the raw material used in this process is high-iron, low-manganese slag. Iron is relatively easy to leach with sulfuric acid, but leaching high-manganese slag is more difficult. In addition, iron and manganese are difficult to separate, and titanium impurities contained in the titanium dioxide waste acid will enter the iron and manganese leaching solution. The leaching solution can be used as a raw material for the composite catalyst, but it cannot produce other products with higher purity. Patent CN117209034A discloses a method for preparing manganese iron oxalate oxide using iron-rich manganese slag as a Cr(VI) removal agent in wastewater. After mixing iron- and manganese-rich slag with sulfuric acid solution to form a slurry, a certain amount of iron powder and oxalic acid are added. After a long period of sedimentation, manganese-iron oxalate composite oxide is formed. This precipitate can be used to remove Cr(VI) from wastewater. However, this process requires a long mixing and sedimentation time, resulting in low reaction efficiency. Furthermore, this method does not achieve the separation and recovery of iron and manganese. The prepared oxide, when used as a wastewater adsorbent, forms new complex smelting slag, creating greater technical difficulties for further recycling. Besides recovering valuable metals, some technical routes employ resource-based methods to prepare low-value-added products for use as building material raw materials in the construction industry. For example, patent document CN105237030A uses manganese-iron slag mixed with phosphate tailings, phosphogypsum, ilmenite slag, cement clinker, additives, etc., to cast-in-place foamed concrete, obtaining concrete blocks or structural layers as building materials. This method consumes a large amount of waste slag resources, but the preparation of building materials requires complex multi-source slag proportioning, limiting the actual amount of slag that can be processed. In addition, it suffers from complex reagents, low added value of the resulting building materials, and low acceptance in related industries.

[0004] Based on existing technologies, how to extract iron and manganese stepwise from low-iron-manganese resources, such as smelting slag from seabed cobalt-manganese oxide ore, and prepare high-value products with high purity remains a technical challenge. It is necessary to develop methods with strong separation effect, high recovery efficiency, simple process flow, and higher product purity to solve the technical problems. Summary of the Invention

[0005] The purpose of this application is to provide a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, in order to solve the above-mentioned problems.

[0006] To achieve the above objectives, the first aspect of this application provides a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, comprising:

[0007] Provides hydrometallurgical slag from seabed cobalt-manganese oxide ore;

[0008] The wet slag from the seabed cobalt-manganese oxide ore, carbon monoxide, and chlorine are first mixed and reacted to obtain a reaction slag, and the flue gas generated during the reaction process is collected.

[0009] The flue gas was condensed and crystallized to obtain ferric chloride;

[0010] The reaction residue was washed with an ether compound, and the washing residue was obtained by solid-liquid separation;

[0011] The washing residue was subjected to water immersion and solid-liquid separation to obtain a manganese chloride solution.

[0012] Optionally, the hydrometallurgical slag from the seabed cobalt-manganese oxide ore is obtained by high-pressure sulfuric acid leaching of seabed cobalt-manganese oxide ore and / or cobalt-rich crust.

[0013] And / or, the iron content in the hydrometallurgical slag of the seabed cobalt-manganese oxide ore is 5-15% by mass, the manganese content is 15-40% by mass, and the silicon content is 5-20% by mass;

[0014] And / or, the average particle size of the hydrometallurgical slag from the seabed cobalt-manganese oxide ore is 20-150 μm.

[0015] Optionally, the chlorine gas accounts for 20%-80% of the total gas volume in the reaction;

[0016] And / or, the carbon monoxide accounts for 20%-80% of the total gas volume of the reaction.

[0017] Optionally, the reaction temperature is 300-600℃ and the time is 1-4h.

[0018] Optionally, the temperature for the condensation and crystallization is 0-30℃;

[0019] And / or, the number of stages of condensation crystallization is 2-3.

[0020] Optionally, the ether compound includes diethyl ether and / or isopropyl ether.

[0021] Optionally, the water immersion temperature is 0-80℃, the liquid-to-solid ratio is 2-10mL / g, the stirring speed is 100-400rpm, and the time is 10-60min.

[0022] Optionally, the manganese chloride solution can be concentrated, evaporated, and crystallized to obtain manganese chloride crystals.

[0023] Optionally, the manganese chloride crystals, the ferric chloride, water, and phosphorus source are mixed and precipitated to obtain manganese iron phosphate.

[0024] Optionally, the phosphorus source includes one or more of ammonium phosphate, ammonium dihydrogen phosphate, and phosphoric acid.

[0025] Compared with the prior art, the beneficial effects of this application include:

[0026] The method for resource recovery of hydrometallurgical slag from seabed cobalt-manganese oxide ore provided in this application achieves an iron and manganese extraction rate of over 95%. The products formed from the iron and manganese are separated stepwise by controlling reaction conditions due to differences in boiling point and vapor pressure, eliminating the problem of unseparable products. The product collection process is simple: iron products can be quickly collected through flue gas condensation, and the reaction slag undergoes a simple washing process to retain manganese chloride. The product can then be collected through dissolution and evaporation crystallization. The iron and manganese products have high purity; the volatilization and condensation of the iron products yields high-purity ferric chloride crystals. Washing with ethers removes other soluble components besides manganese from the reaction slag, retaining high-purity manganese chloride crystals. The obtained iron and manganese products can be used as raw materials for high-value-added products such as lithium iron phosphate cathode materials, effectively solving the technical challenge of stepwise iron and manganese recovery from polymetallic nodule hydrometallurgical slag. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0028] Figure 1 This is a schematic diagram of the process for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore provided in Example 1. Detailed Implementation

[0029] First, the solution provided in this application will be explained in more detail as follows:

[0030] The first aspect of this application provides a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, comprising:

[0031] Provides hydrometallurgical slag from seabed cobalt-manganese oxide ore;

[0032] The wet slag from the seabed cobalt-manganese oxide ore, carbon monoxide, and chlorine are first mixed and reacted to obtain a reaction slag, and the flue gas generated during the reaction process is collected.

[0033] It should be noted that in this step, the iron and manganese in the oxidized ore hydrometallurgical slag undergo a chlorination reaction to transform into ferric chloride (FeCl3) and manganese chloride (MnCl2). The ferric chloride (FeCl3) escapes from the reactor in gaseous form with the reaction flue gas, while the manganese chloride (MnCl2) remains in the reaction slag in solid form. The flue gas is then condensed and crystallized to obtain ferric chloride.

[0034] The reaction residue was washed with an ether compound, and the washing residue was obtained by solid-liquid separation;

[0035] The washing residue was subjected to water immersion and solid-liquid separation to obtain a manganese chloride solution.

[0036] In some embodiments, the hydrometallurgical slag of the seabed cobalt-manganese oxide ore is obtained by high-pressure sulfuric acid leaching of seabed cobalt-manganese oxide ore and / or cobalt-rich crust.

[0037] And / or, the iron content in the hydrometallurgical slag of the seabed cobalt-manganese oxide ore is 5-15% by mass, the manganese content is 15-40% by mass, and the silicon content is 5-20% by mass;

[0038] Optionally, the iron content in the hydrometallurgical slag of seabed cobalt-manganese oxide ore can be any value between 5%, 10%, 15% or 5%-15%, the manganese content can be any value between 15%, 20%, 25%, 30%, 35%, 40% or 15%-40%, and the silicon content can be any value between 5%, 10%, 15%, 20% or 5%-20%.

[0039] It should be noted that the composition of the hydrometallurgical slag from the seabed cobalt-manganese oxide ore differs from that of conventional manganese-iron ore resources. It has low iron and manganese content and high silicon content. Due to the sulfuric acid pressure leaching process, the slag has a high residual sulfur content. Furthermore, the hydrometallurgical slag is non-magnetic and cannot be separated and enriched for iron and manganese through direct beneficiation or other processes.

[0040] And / or, the average particle size of the hydrometallurgical slag from the seabed cobalt-manganese oxide ore is 20-150 μm.

[0041] Optionally, the average particle size of the hydrometallurgical slag from seabed cobalt-manganese oxide ore can be any value between 20μm, 30μm, 60μm, 90μm, 120μm, 150μm, or 20-150μm.

[0042] It should be noted that the beneficial effect of this particle size range is that the residual nickel, cobalt and copper content of the hydrometallurgical slag after the pressure leaching process is very low, and the iron and manganese enrichment is higher, which is conducive to its resource extraction.

[0043] In some embodiments, the chlorine gas accounts for 20%-80% of the total gas volume in the reaction;

[0044] Optionally, chlorine gas accounts for any value between 20%, 30%, 40%, 50%, 60%, 70%, 80% or 20%-80% of the total gas volume of the reaction.

[0045] It should be noted that the volume percentage of chlorine gas must be limited to the range mentioned in this invention. Within this range, ferric chloride (FeCl3) products can be formed, while ensuring the effective conversion efficiency of the reaction and maximizing the reaction effect.

[0046] And / or, the carbon monoxide accounts for 20%-80% of the total gas volume of the reaction.

[0047] Optionally, carbon monoxide accounts for any value between 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 20%-80% of the total gas volume of the reaction.

[0048] In some embodiments, the reaction is carried out at a temperature of 300-600°C for a time of 1-4 hours.

[0049] Optionally, the reaction temperature can be any value between 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃ or 300-600℃, and the time can be any value between 1h, 2h, 3h, 4h or 1-4h.

[0050] It is important to note that the reaction temperature should be limited to the range mentioned in this invention. Within this range, iron and manganese form different product phases, achieving a separation effect. The higher the temperature, the higher the reaction efficiency, the faster the conversion, and the shorter the time required to achieve the desired reaction effect.

[0051] In some embodiments, the temperature of the condensation and crystallization is 0-30°C;

[0052] Optionally, the temperature for condensation and crystallization can be any value between 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, or 0-30℃.

[0053] And / or, the number of stages of condensation crystallization is 2-3.

[0054] In some embodiments, the ether compound includes diethyl ether and / or isopropyl ether.

[0055] Optionally, the reagent can be a mixture of ethers containing one or both of diethyl ether and isopropyl ether.

[0056] It should be noted that the reagents used in this step should be limited to the range of ethers mentioned in this invention. Within this range, the reagents have solubility selectivity and can dissolve impurities other than manganese products, thereby achieving a purification effect and improving the purity of manganese in the water leaching solution in the next step.

[0057] In some embodiments, the water immersion temperature is 0-80℃, the liquid-to-solid ratio is 2-10mL / g, the stirring speed is 100-400rpm, and the time is 10-60min.

[0058] Optionally, the water immersion temperature can be any value between 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, or 0-80℃; the liquid-to-solid ratio can be any value between 2 mL / g, 4 mL / g, 6 mL / g, 8 mL / g, 10 mL / g, or 2-10 mL / g; the stirring speed can be any value between 100 rpm, 200 rpm, 300 rpm, 400 rpm, or 100-400 rpm; and the time can be any value between 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, or 10-60 min.

[0059] In some embodiments, the manganese chloride solution is concentrated, evaporated, and crystallized to obtain manganese chloride crystals.

[0060] In some embodiments, the manganese chloride crystals, the ferric chloride, water, and a phosphorus source are mixed and precipitated to obtain manganese ferric phosphate.

[0061] In some embodiments, the phosphorus source includes one or more of ammonium phosphate, ammonium dihydrogen phosphate, and phosphoric acid.

[0062] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0063] Example 1

[0064] This embodiment provides a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore. The specific process is illustrated below. Figure 1 As shown, the steps are as follows:

[0065] S1: The raw material used is the leaching residue of polymetallic nodules after high-pressure sulfuric acid leaching. The average particle size is 50μm, the iron content is 7wt%, the manganese content is 31wt%, the silicon content is 10wt%, and the nickel, cobalt and copper content is less than 0.01wt%. The raw material is dried at 100℃ for 24h to obtain dried residue.

[0066] S2: Place the dried residue in a chlorination reactor, heat the furnace to 500°C, and introduce a mixture of carbon monoxide and chlorine gas for reaction. Chlorine accounts for 40% of the total gas volume, and the remainder is carbon monoxide. The reaction time is 2 hours. A two-stage condenser is installed at the reactor outlet to condense the flue gas at a condensation temperature of 20°C. Ferric chloride crystals are collected, and the tail gas is discharged after being absorbed by a 30% NaOH solution.

[0067] S3: When the reactor is cooled down, nitrogen atmosphere is introduced for protection. After the atmosphere reaches room temperature, the gas supply is stopped. The residual solid in the reactor is removed, washed in isopropyl ether for 15 minutes, and the solid-liquid separation is achieved by filtration to obtain the washing residue.

[0068] S4: The washing residue was soaked in water at a liquid-to-solid ratio of 4 mL / g, a temperature of 20℃, a soaking time of 30 min, and a stirring speed of 300 rpm. The solid and liquid were separated by filtration, and the water extract was evaporated and crystallized at 200℃ to obtain manganese chloride crystals.

[0069] In this embodiment, the recovery rates of iron and manganese are 96% and 95%, respectively.

[0070] Example 2

[0071] This embodiment provides a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, the specific steps of which are as follows:

[0072] S1: The raw material used is the leaching residue of cobalt-rich crust after high-pressure sulfuric acid leaching. The average particle size is 120μm, the iron content is 13 wt%, the manganese content is 26 wt%, the silicon content is 12 wt%, and the nickel, cobalt and copper content is less than 0.01 wt%. It is dried at 100℃ for 48h to obtain dried residue.

[0073] S2: Place the dried residue in a chlorination reactor, heat the furnace to 380°C, and introduce a mixture of carbon monoxide and chlorine gas for reaction. Chlorine accounts for 70% of the total gas volume, and the remainder is carbon monoxide. The reaction time is 3 hours. A two-stage condenser is installed at the reactor outlet to condense the flue gas at a condensation temperature of 30°C. Ferric chloride crystals are collected, and the tail gas is discharged after being absorbed by a 30% NaOH solution.

[0074] S3: When the reactor is cooled down, nitrogen atmosphere is introduced for protection. After the atmosphere reaches room temperature, the gas supply is stopped. The residual solid in the reactor is removed, washed in ether for 25 minutes, filtered to separate the solid and liquid, and the washing residue is obtained.

[0075] S4: The washing residue was soaked in water at a liquid-to-solid ratio of 5 mL / g, a temperature of 25℃, a soaking time of 60 min, and a stirring speed of 400 rpm. The solid and liquid were separated by filtration. The water-soaked solution was evaporated at 200℃ to obtain manganese chloride crystals.

[0076] In this embodiment, the recovery rates of iron and manganese were 94% and 93%, respectively.

[0077] Example 3

[0078] This embodiment provides a method for the stepwise recovery of iron and manganese from hydrometallurgical slag of seabed cobalt-manganese oxide ore, as detailed below:

[0079] S1: The raw material used is a mixture of leaching residue from cobalt-rich crusts and polymetallic nodules after high-pressure sulfuric acid leaching. The ratio of the two residues is 1:1, the average particle size is 100μm, the iron content is 10wt%, the manganese content is 28wt%, the silicon content is 8wt%, and the nickel, cobalt and copper content is less than 0.01wt%. The residue is dried at 100℃ for 24h to obtain dried residue.

[0080] S2: Place the dried residue in a chlorination reactor, heat the furnace to 575°C, and introduce a mixture of carbon monoxide and chlorine gas for reaction. Chlorine accounts for 25% of the total gas volume, and the remainder is carbon monoxide. The reaction time is 1.5 hours. A three-stage condenser is installed at the reactor outlet to condense the flue gas at a condensation temperature of 20°C. Ferric chloride crystals are collected, and the tail gas is discharged after being absorbed by a 30% NaOH solution.

[0081] S3: When the reactor is cooled down, nitrogen atmosphere is introduced for protection. After the atmosphere reaches room temperature, the gas supply is stopped. The residual solid in the reactor is removed, washed in isopropyl ether for 25 minutes, filtered to separate solid and liquid, and the washing residue is obtained.

[0082] S4: The washing residue was leached in water at a liquid-to-solid ratio of 4 mL / g, a temperature of 20℃, a leaching time of 30 min, and a stirring speed of 250 rpm. After solid-liquid separation by filtration, the water leaching solution was evaporated and crystallized at 200℃ to collect manganese chloride crystals.

[0083] In this embodiment, the iron and manganese recovery rates are 97% and 97%, respectively.

[0084] Example 4

[0085] This embodiment provides a method for the resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, the specific steps of which are as follows:

[0086] S1: The raw material used is the leaching residue of polymetallic nodules after high-pressure sulfuric acid leaching. The average particle size is 30μm, the iron content is 8 wt%, the manganese content is 35wt%, the silicon content is 6 wt%, and the nickel, cobalt and copper content is less than 0.01 wt%. It is naturally dried for 120h to obtain dried residue.

[0087] S2: Place the dried residue in a chlorination reactor, heat the furnace to 450°C, and introduce a mixture of carbon monoxide and chlorine gas for reaction. Chlorine accounts for 35% of the total gas volume, and the remainder is carbon monoxide. The reaction time is 2 hours. A two-stage condenser is installed at the reactor outlet to condense the flue gas at a condensation temperature of 20°C. Ferric chloride crystals are collected, and the tail gas is discharged after being absorbed by a 30% NaOH solution.

[0088] S3: When the reactor is cooled down, nitrogen atmosphere is introduced for protection. After the atmosphere is turned off at room temperature, the residual solid in the reactor is removed and washed in a mixed solution of isopropyl ether and diethyl ether for 30 minutes. The solid and liquid are separated by filtration to obtain the washing residue.

[0089] S4: The washing residue was soaked in water at a liquid-to-solid ratio of 3 mL / g, a temperature of 20℃, a soaking time of 60 min, and a stirring speed of 350 rpm. After solid-liquid separation by filtration, the water extract was evaporated and crystallized at 200℃ to collect manganese chloride crystals.

[0090] In this embodiment, the iron and manganese recovery rates are 95% and 94%, respectively. The recovered ferric chloride and manganese chloride crystals are mixed in a manganese-iron molar ratio of 6:4, dissolved in pure water, added to an ammonium phosphate solution with pH adjusted to 5, stirred to precipitate, filtered for solid-liquid separation, dried at 100s℃, and calcined at 500s℃ to obtain the manganese-iron phosphate precursor.

[0091] Comparative Example 1

[0092] The difference from Example 1 is that chlorine is not added in step S2.

[0093] In this comparative example, the recovery rates of iron and manganese were 0% and 0%, respectively.

[0094] Comparative Example 2

[0095] The difference from Example 1 is that in step S2, the volume of chlorine gas accounts for 100% of the total volume.

[0096] In this comparative example, the recovery rates of iron and manganese were 30% and 5%, respectively.

[0097] Furthermore, since the iron and manganese products were not separated, additional steps are needed to extract the iron and manganese and purify the products.

[0098] Comparative Example 3

[0099] The difference from Example 1 is that the reaction temperature in step S2 is 800°C.

[0100] In this comparative example, the recovery rates of iron and manganese were 82% and 70%, respectively.

[0101] Comparative Example 4

[0102] The difference from Example 1 is that in step S3, the washing solution is an aqueous solution.

[0103] In this comparative example, the manganese product was dissolved together with other chlorinated components. The manganese chloride crystals had low purity, requiring an additional product purification process.

[0104] analyze:

[0105] As can be seen from the above results, the raw materials described in this invention require the aforementioned steps and conditions, including the gas composition, temperature range, and washing solvent, to achieve the beneficial effects of this invention. Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0106] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore, characterized in that, include: Provides hydrometallurgical slag from seabed cobalt-manganese oxide ore; The wet slag from the seabed cobalt-manganese oxide ore, carbon monoxide, and chlorine are first mixed and reacted to obtain a reaction slag, and the flue gas generated during the reaction process is collected. The flue gas was condensed and crystallized to obtain ferric chloride; The reaction residue was washed with an ether compound, and the washing residue was obtained by solid-liquid separation; The washing residue was subjected to water immersion and solid-liquid separation to obtain a manganese chloride solution. The hydrometallurgical slag of the seabed cobalt-manganese oxide ore is obtained by high-pressure sulfuric acid leaching of seabed cobalt-manganese oxide ore and / or cobalt-rich crust. The iron content in the hydrometallurgical slag from the seabed cobalt-manganese oxide ore is 5-15%, the manganese content is 15-40%, and the silicon content is 5-20%. The average particle size of the hydrometallurgical slag from the seabed cobalt-manganese oxide ore is 20-150 μm. The chlorine gas accounts for 20%-80% of the total gas volume in the reaction; The carbon monoxide accounts for 20%-80% of the total gas volume in the reaction; The reaction is carried out at a temperature of 300-600℃ for 1-4 hours. The temperature for the condensation and crystallization is 0-30℃.

2. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to claim 1, characterized in that, The number of stages of condensation crystallization is 2-3.

3. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to claim 1, characterized in that, The ether compounds include diethyl ether and / or isopropyl ether.

4. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to claim 1, characterized in that, The water immersion temperature is 0-80℃, the liquid-to-solid ratio is 2-10mL / g, the stirring speed is 100-400rpm, and the time is 10-60min.

5. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to any one of claims 1-4, characterized in that, The manganese chloride solution was concentrated, evaporated, and crystallized to obtain manganese chloride crystals.

6. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to claim 5, characterized in that, The manganese chloride crystals, the ferric chloride, water, and phosphorus source are mixed and precipitated to obtain manganese iron phosphate.

7. The method for resource utilization of hydrometallurgical slag from seabed cobalt-manganese oxide ore according to claim 6, characterized in that, The phosphorus source includes one or more of ammonium phosphate, ammonium dihydrogen phosphate, and phosphoric acid.

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