CN114621080B - Method for preparing iron manganese oxalate by using high-iron manganese oxide ore - Google Patents
Method for preparing iron manganese oxalate by using high-iron manganese oxide ore Download PDFInfo
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- CN114621080B CN114621080B CN202210246992.0A CN202210246992A CN114621080B CN 114621080 B CN114621080 B CN 114621080B CN 202210246992 A CN202210246992 A CN 202210246992A CN 114621080 B CN114621080 B CN 114621080B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B47/00—Obtaining manganese
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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
Abstract
The invention discloses a method for preparing iron manganese oxalate by using high-iron manganese oxide ore, which comprises the following steps: leaching manganese in ore: mixing oxalic acid/ferric oxalate mixed solution serving as a leaching agent with high-iron manganese oxide to prepare slurry, and performing solid-liquid separation after leaching to obtain iron-containing slag and a first separation solution; reducing and depositing iron and manganese: reducing the separation liquid I, and performing solid-liquid separation to obtain iron and manganese oxalate precipitate and a separation liquid II; and (3) recovering iron and manganese oxalate: washing and drying the iron and manganese oxalate precipitate to obtain pure iron and manganese oxalate; preparing a leaching agent: adding oxalic acid into the second separation liquid to obtain a mixed solution, pulping the mixed solution and the iron-containing slag, performing solid-liquid separation after leaching to obtain leached waste residues and a mixed solution containing oxalic acid/ferric oxalate, and returning the mixed solution containing oxalic acid/ferric oxalate to be reused to form a circulation process. The preparation method can effectively solve the problems of high cost and large pollutant discharge amount in the existing method, and can realize the resource utilization of the high-iron manganese oxide ore.
Description
Technical Field
The invention relates to the technical field of resource utilization of high-iron manganese ores, in particular to a method for preparing iron manganese oxalate by utilizing high-iron manganese oxide ores.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, small environmental pollution, no memory effect and the like, and becomes an important foundation for supporting the development of the current power supply for the electric automobile. Lithium iron phosphate, one of the mainstream batteries in the electric vehicle market at present, is excellent in safety and cycle life, but has low conductivity and low bulk density, and thus has become a short plate limiting the development thereof. The lithium iron manganese phosphate is a novel battery material obtained by adding a manganese element into a lithium iron phosphate battery, has a higher voltage platform, has a theoretical energy density 15-20% higher than that of lithium iron phosphate under equivalent conditions, and is considered as an upgraded version of the lithium iron phosphate.
Manganese and iron are important raw materials for producing the lithium manganese iron phosphate battery. Although the reserves of iron ores and manganese ores in China are relatively rich, lean ores are mainly used, wherein the average grade of iron ores is 32 percent and is 11 percent lower than the average grade in the world, the average grade of manganese ores in the whole country is about 20 percent, and the reserve of rich manganese ores (manganese oxide ores contain more than 30 percent of manganese and manganese carbonate ores contain more than 25 percent of manganese) only accounts for 6.4 percent. Because the geochemical behaviors of iron and manganese are similar, the iron and manganese are closely symbiotic in the geological process, the ratio of high-iron manganese ore (Mn/Fe is less than or equal to 3) is 35.18 percent in the found main manganese ore in China, and other iron and manganese ore (Mn/Fe is less than or equal to 1) is thousands of tons. The separation of manganese and iron in the ferro-manganese ore is difficult, the extraction and utilization difficulty is high, and the synchronous resource utilization of ferromanganese is difficult to realize.
The iron manganese oxalate is a high-quality precursor for preparing the lithium iron manganese phosphate, and is mainly obtained by mixing and precipitating commercial manganese salt, iron salt and oxalate at present. The technology firstly needs to obtain commercial manganese salt and iron salt from the ferromanganese ore through a complex metallurgical process, and has the advantages of long process flow, high cost and large pollutant discharge amount.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing iron manganese oxalate by using high-iron manganese oxide ore, which can effectively solve the problems of high cost and large pollutant discharge amount in the existing method and can realize resource utilization of the high-iron manganese ore.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is as follows:
a method for preparing iron manganese oxalate by using high-iron manganese oxide ore comprises the following steps:
(1) Leaching manganese in ore: mixing oxalic acid/ferric oxalate mixed solution serving as a leaching agent with high-iron manganese oxide to prepare slurry, and performing solid-liquid separation after leaching to obtain iron-containing slag and a first separation solution;
(2) Reducing and depositing iron and manganese: reducing the separation liquid I obtained in the step (1), and performing solid-liquid separation to obtain an iron manganese oxalate precipitate and a separation liquid II;
(3) And (3) recovering iron and manganese oxalate: washing and drying the iron and manganese oxalate precipitate obtained in the step (2) to obtain pure iron and manganese oxalate;
(4) Preparing a leaching agent: and (3) supplementing oxalic acid to the second separation liquid in the step (2) to obtain a mixed solution, then slurrying the mixed solution with the iron-containing slag in the step (1), performing solid-liquid separation after leaching to obtain leached waste residues and a mixed solution containing oxalic acid/ferric oxalate, and returning the mixed solution containing oxalic acid/ferric oxalate to the step (1) for reuse to form a circulation process.
Further, the granularity of the high-iron manganese oxide ore in the step (1) is more than or equal to 100 meshes.
Further, the liquid-solid ratio of the oxalic acid/ferric oxalate mixed solution to the high-iron manganese oxide ore in the step (1) is 1-10.
Further, the leaching temperature in the step (1) is more than or equal to 30 ℃, and the leaching time is more than or equal to 0.5h.
Further, the reduction method of the first separation liquid in the step (2) comprises the following steps: and (5) carrying out ultraviolet irradiation on the first separation liquid to realize reduction.
In the above scheme, if the ultraviolet irradiation intensity is high, the irradiation time can be relatively shortened, and if the ultraviolet irradiation intensity is low, the irradiation time needs to be correspondingly prolonged.
Further, the reduction method of the first separation liquid in the step (2) comprises the following steps: a reducing agent made of carbon and hydrogen is added thereto.
Further, the reducing agent includes ascorbic acid, citric acid, or malic acid.
Further, the amount of oxalic acid added in step (4) is calculated by the following formula:
further, the leaching temperature of the iron-containing slag in the step (4) is 70-100 ℃, and the leaching time is more than or equal to 3h.
In step (1) of the scheme of the present application, the iron oxalate in the leaching agent exists in the form of a complex, and the form of the complex is determined by the ratio relationship between the ferric iron and the oxalate ions, and the specific complex form is as follows:
in the manganese oxide ore with high iron in the step (1) of the scheme, iron mainly exists in the form of ferric oxide, and manganese mainly exists in the form of trivalent and tetravalent manganese oxides.
In the manganese leaching process of the ore in the step (1), the chemical reaction of leaching manganese in the ore by oxalic acid is as follows:
in the leaching process, mnO is rapidly leached by oxalic acid through liquid-solid reaction 2 Formation of Mn 2+ At the same time, an equal amount of oxalic acid is converted to CO 2 The oxalic acid concentration in the solution is reduced (formula (1)). Is subjected to MnC 2 O 4 Limitation of solubility, mn in solution 2+ And free C 2 O 4 2- Combining to generate MnC attached to the surface of pyrolusite slag 2 O 4 The free oxalic acid concentration is further reduced (formula (2)).
As the leaching reaction proceeds, oxalic acid passes through the pyrolusite surface MnC 2 O 4 The solid layer diffuses into the ore and Fe 2 O 3 The contact improves the Fe extraction rate (formula (3)).
Leached Fe 3+ And C 2 O 4 2- Combined, converted into [ Fe (C) 2 O 4 ) n ] (3-2n)+ The free C in the leaching solution is reduced 2 O 4 2- Concentration of (1), (6), (7)).
With free C 2 O 4 2- Reduction in concentration, mnC 2 O 4 Is decomposed into Mn 2+ And C 2 O 4 2- The leaching rate of Mn increases (formula (8)).
In the scheme, the smaller the particle size of the ore is, the larger the specific surface area is, the larger the contact area with the leaching agent is, and the higher the leaching rate is. However, the smaller the particle size of the ore is, the higher the energy consumption for crushing the ore is, so that the particle size of the manganese ore is not less than 100 meshes in comprehensive consideration. The reaction speed of oxalic acid and manganese oxide is very fast and can be carried out at normal temperature, so the temperature of the leaching process is controlled to be not lower than 30 ℃, and the leaching time is not lower than 0.5h.
In addition, when the iron manganese oxalate with the same quality is produced, the higher the manganese concentration in the leachate is, the smaller the flow of the required solution is, the smaller the production equipment is, and the lower the cost is; however, the higher the manganese concentration in the leachate, the higher the viscosity of the solution, the poorer the leaching effect, and when the manganese concentration exceeds the solubility thereof, the manganese is converted into crystal precipitate, so that the manganese recovery rate is reduced. Therefore, the manganese concentration in the leachate is respectively controlled to be 40-100 g/L, the calculation is carried out according to the range of the manganese content in the ore being 10-40%, and the solid-to-liquid ratio (volume-mass ratio) of ore pulp prepared by the mixed solution and the manganese ore is 1-10:1.
in the scheme, the key steps of the iron and manganese oxalate produced in the step (2) are to reduce ferric iron into ferrous iron, reduce the amount of a ferric iron complex, increase free oxalate radicals in a solution and promote ferrous ions and manganese ions to be converted into iron and manganese oxalate precipitates. The reduction treatment method can adopt the following two methods:
(1) the reduction of ferric iron to ferrous iron is carried out by ultraviolet/solar radiation.
(2) Adding any reducing agent which is composed of carbon and hydrogen and can reduce ferric iron into ferrous iron, such as ascorbic acid, citric acid or malic acid. Theoretically, all substances capable of reducing ferric iron into ferrous iron can be adopted, but the process is a circulating process, other impurities and elements brought by a reducing agent can be accumulated in the circulating process, the solution viscosity is increased, the leaching process is influenced, and meanwhile, the quality of the iron manganese oxalate is reduced due to the increase of the impurity content. Therefore, the reducing agent consisting of carbon and hydrogen is preferred in the step, and during the reaction process, carbon in the reducing agent is converted into carbon dioxide and hydrogen is converted into water, so that other impurities are not left.
In the above technical solution, oxalic acid is required to be added in the step (4) to supplement consumption of oxalic acid due to leaching and reduction processes. The amount of oxalic acid added is calculated by the following formula:
in the above technical scheme, in the step (4), the chemical reaction in the iron leaching process is as follows:
the reaction rate of the process is increased along with the increase of the temperature, the increase of the temperature can accelerate the leaching rate of the iron, shorten the leaching time and reduce the volume of a leaching reactor, so the reaction temperature of the leaching process can be controlled within 70 to 100 ℃, and the leaching time is preferably not less than 3h.
The beneficial effects produced by the invention are as follows:
the invention takes the high-iron manganese oxide ore as the raw material to directly synthesize the iron and manganese oxalate, thereby realizing the synchronous high-efficiency resource utilization of iron and manganese in the high-iron manganese ore.
The invention adopts a mode of iron and manganese graded leaching, so that the concentration of substances in the solution is in the optimal range, the leaching and recovery efficiency of ferromanganese is improved, the final leaching rate of iron can reach 97.10%, the leaching rate of manganese can reach 100%, and the purpose of efficiently leaching iron and manganese is realized, and the specific principle is as follows:
(1) At C 2 O 4 2- With Fe 3+ Is carried out by leaching the iron-rich slag at high temperature by presoaking manganese under the condition that the molar ratio of (3) is kept in H 2 C 2 O 4 Excess and MnC 2 O 4 And under the condition of no precipitation, the complete leaching of iron is realized.
(2) Uses the oxalic acid iron solution with slightly excessive oxalic acid to leach the pyrolusite, realizes the high-efficiency leaching of Mn, further consumes C 2 O 4 2- While allowing oxalate in the solution to be in the form of iron oxalate complex, free C 2 O 4 2- The concentration is reduced, and Mn is equal to Mn 2+ Is present in the form of (B) to obtain a compound containing Mn 2+ And leachate of iron oxalate complex.
The invention directly synthesizes the iron and manganese oxalate by the high-iron manganese oxide ore, saves the production process of manganese salt and iron salt, shortens the process flow and can greatly reduce the production cost of the iron and manganese oxalate.
The invention is a closed cycle process, the leachate is recycled, no wastewater is discharged, the clean production level is high, and the environmental protection benefit is remarkable.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
A method for preparing iron manganese oxalate by using high-iron manganese oxide ore comprises the following steps:
(1) Leaching manganese in ore: mixing oxalic acid/ferric oxalate mixed solution serving as a leaching agent with the high-iron manganese oxide ore to prepare slurry, wherein the slurry liquid-solid ratio (volume-mass ratio) is 5:1, and under the stirring condition, the reaction temperature is maintained at 40 ℃ and the reaction time is 1 h, so that manganese in the high-iron manganese oxide ore is converted into soluble manganese ions;
(2) Liquid-solid separation: carrying out filter pressing separation on the slurry obtained in the step (1) to obtain iron-containing slag and a first separation solution containing oxalate, ferric iron and divalent manganese ions;
(3) Reducing and depositing iron and manganese: carrying out ultraviolet radiation on the separation liquid I obtained in the step (2) to reduce ferric ions into ferrous ions, and obtaining iron manganese oxalate precipitate; carrying out centrifugal separation to obtain iron manganese oxalate precipitate and a second separation solution containing oxalic acid;
(4) And (3) recovering iron and manganese oxalate: washing the iron and manganese oxalate precipitate obtained in the step (3), and drying at 110 ℃ for 2h to obtain a pure iron and manganese oxalate product;
(5) Preparing a leaching agent: adding oxalic acid into the oxalic acid separation liquid II obtained in the step (3), wherein the adding amount of the oxalic acid is calculated according to the following formula:
(6) Leaching iron from manganese slag: mixing the leaching agent obtained in the step (5) with the iron-containing slag obtained in the step (2), and reacting for 5h at 90 ℃ to convert iron in the iron-containing slag into soluble ferric ions;
(7) Liquid-solid separation: performing filter pressing separation on the slurry obtained in the step (6) to obtain leached waste residues and a separation solution containing an oxalic acid/ferric oxalate mixed solution;
(8) Solution circulation: and (4) returning the oxalic acid-containing separation liquid obtained in the step (7) to the step (1) to leach manganese in the high-iron manganese ore to form a circulating process.
Example 2
A method for preparing iron manganese oxalate by using high-iron manganese oxide ore comprises the following steps:
(1) Leaching manganese in ore: mixing oxalic acid/ferric oxalate mixed solution serving as a leaching agent with the high-iron manganese oxide ore to prepare slurry, wherein the slurry liquid-solid ratio (volume-mass ratio) is 8:1, and under the stirring condition, the reaction temperature is kept at 35 ℃ and the reaction time is 0.5h, so that manganese in the high-iron manganese oxide ore is converted into soluble manganese ions;
(2) Liquid-solid separation: performing filter pressing separation on the slurry obtained in the step (1) to obtain iron-containing slag and a first separation solution containing oxalate, ferric iron and divalent manganese ions;
(3) Reducing and depositing iron and manganese: adding ascorbic acid into the separation liquid I obtained in the step (2) to reduce ferric ions into ferrous ions, so as to obtain iron manganese oxalate precipitate; carrying out centrifugal separation to obtain iron and manganese oxalate precipitate and a second separation solution containing oxalic acid;
(4) And (3) recovering iron and manganese oxalate: washing the iron and manganese oxalate precipitate obtained in the step (3), and drying at 100 ℃ for 2.5 h to obtain a pure iron and manganese oxalate product;
(5) Preparing a leaching agent: adding oxalic acid into the second oxalic acid-containing separation liquid obtained in the step (3), wherein the adding amount of the oxalic acid is calculated according to the following formula:
(6) Leaching iron from manganese slag: mixing the leaching agent obtained in the step (5) with the iron-containing slag obtained in the step (2), and reacting for 4 h at 96 ℃ to convert iron in the iron-containing slag into soluble ferric ions;
(7) Liquid-solid separation: performing filter pressing separation on the slurry obtained in the step (6) to obtain leached waste residues and a separation solution containing an oxalic acid/ferric oxalate mixed solution;
(8) Solution circulation: and (4) returning the separation liquid containing oxalic acid obtained in the step (7) to the step (1) to leach manganese in the high-iron manganese ore to form a circulating process.
Comparative example 1
A method for preparing iron manganese oxalate by using high-iron manganese oxide ore comprises the following steps:
(1) Mixing oxalic acid solution serving as a leaching agent with the high-iron manganese oxide ore to prepare slurry, wherein the liquid-solid ratio (volume-mass ratio) of the slurry is 5:1, maintaining the reaction temperature at 40 ℃ and the reaction time at 1 h under the stirring condition, then carrying out liquid-solid separation, and collecting separation liquid;
(2) And (3) carrying out ultraviolet irradiation on the separation liquid, and then carrying out solid-liquid separation to obtain iron and manganese oxalate precipitates and the separation liquid.
Test examples
The high-iron manganese oxide ore is averagely divided into 3 parts, each 1000 kg, the ore leaching operation is carried out according to the methods in the examples 1-2 and the comparative example 1 respectively, the final leaching rates of iron and manganese are calculated, and the specific results are shown in the table 1.
Table 1: statistics of leaching results
| Iron leaching rate | Leaching rate of manganese | |
| Example 1 | 97.5% | 99.3% |
| Example 2 | 98.2% | 99.5% |
| Comparative example 1 | 91.5% | 67.4% |
As can be seen from the data in the above table, the iron leaching rate and the manganese leaching rate were higher than those in comparative example 1 by the methods in examples 1 to 2.
Claims (8)
1. A method for preparing iron manganese oxalate by using high-iron manganese oxide ore is characterized by comprising the following steps:
(1) Leaching manganese in ore: mixing oxalic acid/ferric oxalate mixed solution serving as a leaching agent with high-iron manganese oxide to prepare slurry, and performing solid-liquid separation after leaching to obtain iron-containing slag and a first separation solution;
(2) Reducing and depositing iron and manganese: reducing the first separation liquid obtained in the step (1), and performing solid-liquid separation to obtain iron manganese oxalate precipitate and a second separation liquid;
(3) And (3) recovering iron and manganese oxalate: washing and drying the iron and manganese oxalate precipitate obtained in the step (2) to obtain pure iron and manganese oxalate;
(4) Preparation of leaching agent and iron leaching of manganese slag: and (3) adding oxalic acid into the second separation liquid in the step (2) to obtain a mixed solution, wherein the adding amount of the oxalic acid is calculated by the following formula:
2. The method for preparing manganous iron oxalate from high-iron manganese oxide ore according to claim 1, wherein the granularity of the high-iron manganese oxide ore in the step (1) is more than or equal to 100 meshes.
3. The method for preparing the iron-manganese oxalate by using the high-iron manganese oxide ore according to claim 1, wherein the liquid-solid ratio of the oxalic acid/iron oxalate mixed solution to the high-iron manganese oxide ore in the step (1) is 1-10.
4. The method for preparing the iron and manganese oxalate by using the high-iron manganese oxide ore according to claim 1, wherein the leaching temperature in the step (1) is not less than 30 ℃, and the leaching time is not less than 0.5h.
5. The method for preparing iron and manganese oxalate from high-iron manganese oxide ore according to claim 1, wherein the reduction method of the first separation solution in the step (2) comprises the following steps: and (4) carrying out ultraviolet irradiation on the first separation liquid to realize reduction.
6. The method for preparing iron and manganese oxalate from high-iron manganese oxide ore according to claim 1, wherein the reduction method of the first separation solution in the step (2) comprises the following steps: a reducing agent made of carbon and hydrogen is added thereto.
7. The method for preparing iron-manganese oxalate using high-iron manganese oxide ore according to claim 6, wherein the reducing agent comprises ascorbic acid, citric acid or malic acid.
8. The method for preparing the iron and manganese oxalate by using the high-iron manganese oxide ore according to claim 1, wherein the leaching temperature of the iron-containing slag in the step (4) is 70-100 ℃, and the leaching time is not less than 3h.
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| JPH11209828A (en) * | 1998-01-23 | 1999-08-03 | Agency Of Ind Science & Technol | Method for recovering rare-earth oxide |
| CN106025282A (en) * | 2016-06-08 | 2016-10-12 | 闫春燕 | High-purity ultrafine oxalate ferromanganese and preparation method thereof |
| CN107502740A (en) * | 2017-06-26 | 2017-12-22 | 四川大学 | One kind reclaims iron resource method from pyrolusite leached mud |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN113293314A (en) * | 2021-05-31 | 2021-08-24 | 湘潭大学 | Method for leaching and separating bismuth from blast furnace gas ash or/and mud |
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|---|---|---|---|---|
| JPH11209828A (en) * | 1998-01-23 | 1999-08-03 | Agency Of Ind Science & Technol | Method for recovering rare-earth oxide |
| CN106025282A (en) * | 2016-06-08 | 2016-10-12 | 闫春燕 | High-purity ultrafine oxalate ferromanganese and preparation method thereof |
| CN107502740A (en) * | 2017-06-26 | 2017-12-22 | 四川大学 | One kind reclaims iron resource method from pyrolusite leached mud |
| CN111908442A (en) * | 2020-08-07 | 2020-11-10 | 上海华谊（集团）公司 | Ferromanganese phosphate, lithium iron manganese phosphate and preparation method thereof |
| CN113293314A (en) * | 2021-05-31 | 2021-08-24 | 湘潭大学 | Method for leaching and separating bismuth from blast furnace gas ash or/and mud |
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