CN113463134B - Process method for producing electrolytic manganese metal by using silicomanganese slag - Google Patents
Process method for producing electrolytic manganese metal by using silicomanganese slag Download PDFInfo
- Publication number
- CN113463134B CN113463134B CN202110772841.4A CN202110772841A CN113463134B CN 113463134 B CN113463134 B CN 113463134B CN 202110772841 A CN202110772841 A CN 202110772841A CN 113463134 B CN113463134 B CN 113463134B
- Authority
- CN
- China
- Prior art keywords
- slag
- manganese
- powder
- silicomanganese
- process method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of manganese processing, and relates to a process method for producing electrolytic manganese metal by utilizing silicomanganese slag. The process method comprises the following steps of 1, raw material preparation: crushing silicomanganese slag into silicomanganese slag powder; 2. pulping and leaching: pulping with anolyte, and leaching with concentrated sulfuric acid; 3. mixing with mineral powder: filter pressing, mixing the filtrate with the mineral powder; 4. acid collection and impurity removal: adding baking powder for acid recovery, adding ammonia water for neutralization, adding hydrogen peroxide and introducing air to remove iron ions, and adding SDD to remove heavy metals; 5. purifying: filter pressing, namely adding a flocculating agent and active carbon into the filtrate, standing and filter pressing; 6. electrolysis: obtaining the manganese metal. The process method enables industrial solid waste silicomanganese slag generated in the production process of silicomanganese alloy to be recycled, reduces resource waste, reduces environmental pollution, protects environment, saves land, extends manganese processing industrial chain and widens utilization approach of silicomanganese slag.
Description
Technical Field
The invention belongs to the technical field of manganese processing, and relates to a process method for producing electrolytic manganese metal by utilizing silicomanganese slag.
Background
The existing production of silicon-manganese alloy adopts a pyrometallurgical process; in the production process of the silicon-manganese alloy, industrial solid waste silicon-manganese slag with the manganese content of 6-10% is inevitably generated. About 1 ton of silicomanganese slag is generated when 1 ton of silicomanganese is produced, and therefore, the accumulative amount of the silicomanganese slag reaches hundreds of millions of tons calculated according to more than 1000 million tons of silicomanganese produced by the pyrometallurgical industry of China every year.
The silicomanganese slag is relatively complex in composition and structure, most of the silicomanganese slag is piled as solid waste, and the long-time piling can seriously pollute the environment, occupy the land and waste resources; or, part of the manganese-containing silicon-manganese slag is used in the building material industry, microcrystalline glass and the like, but the manganese element is not recycled due to poor technical feasibility, or the silicon-manganese slag is limited in consumption, so that the manganese-containing silicon-manganese slag cannot be industrially popularized; meanwhile, if the treatment is improper, the environmental pollution is easily caused to a certain extent, and environmental protection pressure and resource waste are caused.
The silicon-manganese slag is analyzed, so that the total manganese content of the silicon-manganese slag is 6% -10%, and the silicon-manganese slag is converted into about 1.5-3 ten thousand tons of simple substance manganese calculated according to about 30 ten thousand tons of anode slag generated by silicon-manganese alloy every year; the huge amount of manganese element can not be effectively utilized, thereby invisibly causing manganese resource waste and restricting the development of metallurgical industry; in addition, the silicomanganese slag contains various recyclable element components, and long-term storage is also great waste of resources, which violates the national sustainable development concept; in addition, the silicomanganese slag can generate hydrogen sulfide gas under an acidic condition, has toxicity, cannot be effectively eliminated by the prior art, and has adverse effects on the environment.
In addition, a large amount of anode slag is generated in the process of manganese electrolysis; the traditional treatment idea of the anode slag is mainly that the anode slag directly reacts by contacting with flue gas sulfur dioxide in a counter-potential manner; however, these techniques have not been industrially popularized due to poor feasibility, poor reaction effect, high discharged tetravalent manganese, or limited consumption of electrolytic manganese slag.
Disclosure of Invention
The invention aims to provide a process method for producing electrolytic manganese metal by utilizing silicomanganese slag, which can recover manganese element in the silicomanganese slag maximally, optimally and economically, effectively eliminate hydrogen sulfide gas generated in the reaction process, reduce resource waste and promote sustainable development.
The technical scheme of the invention for solving the technical problems is as follows.
A process method for producing electrolytic manganese metal by utilizing silicomanganese slag comprises the following process steps:
(1) Preparing raw materials: the raw material comprises silicomanganese slag; crushing silicomanganese slag generated in the processing process of silicomanganese alloy into silicomanganese slag powder, and using the silicomanganese slag powder as raw material slag powder;
(2) Pulping and leaching: mixing and stirring raw material slag powder and anolyte generated in the process of electrolyzing metal manganese, performing pulping reaction, and adding concentrated sulfuric acid for leaching reaction;
(3) Mixing with mineral powder: performing filter pressing on the materials after pulping and leaching, and mixing the obtained filtrate with mineral powder to obtain a mixed solution; wherein the mineral powder is manganese carbonate mineral powder or manganese oxide mineral powder;
(4) Acid collection and impurity removal: adding baking powder into the mixed solution for acid recovery treatment, and adding ammonia water for neutralization reaction when the residual acid is reduced to below 2 g/L; when the pH value of the system reaches 6.7-7.2, adding hydrogen peroxide and introducing air simultaneously to remove iron ions in the system, and adding SDD to remove heavy metals in the system;
(5) Purifying: performing filter pressing on the material obtained in the step (4), adding a flocculating agent and active carbon into the obtained filtrate, stirring, standing for a certain time, and performing filter pressing on the upper-layer liquid again to obtain a filtrate;
(6) Electrolysis: and (4) feeding the filtrate obtained in the step (5) as a neutral solution to an electrolytic manganese process for electrolysis to obtain metal manganese.
According to the technical scheme, the silicomanganese slag is subjected to a series of processes of pulping and leaching, mixing with manganese ore, impurity removal and purification, preparation of neutral solution electrolysis and the like, and the silicomanganese slag generated in the silicomanganese alloy processing process is treated, recycled and utilized, so that the resource waste of the silicomanganese slag is reduced, the pollution to the environment is reduced, the occupied space of waste stockpiling is reduced, and good economic benefits are brought.
Further, in the step (1) of the process method, the raw materials also comprise anode slag; drying and crushing anode slag generated in the process of electrolyzing metal manganese into anode slag powder, and mixing silicon-manganese slag powder and the anode slag powder to be used as raw material slag powder. By adding the anode slag into the raw materials, on one hand, the manganese dioxide in the anode slag can be used for treating sulfide, and on the other hand, the anode slag waste generated in the process of electrolyzing the metal manganese can be utilized.
Further, in the step (1) of the process method, the silicomanganese slag is crushed into silicomanganese slag powder with the particle size of less than 100 meshes by using a roller press, and the anode slag is dried and then crushed into anode slag powder with the particle size of less than 100 meshes by using the roller press. By the processing method, the silicomanganese slag and the anode slag are processed into raw material slag powder with reasonable particle size, so that smooth proceeding of subsequent processes is ensured.
Further, in the process method, the anode slag and the silicomanganese slag are mixed according to the mass ratio of 1 (8-10).
Further, in the process method, the mass ratio of the raw material slag powder to the mineral powder is as follows: the mineral powder is 2.
Further, in the process method, the mass ratio of the raw material slag powder, the mineral powder and the anolyte is (raw material slag powder + mineral powder): the anolyte is 1 (10-15); under the proportion range, the slurry after pulping can better carry out the subsequent leaching reaction.
Further, in the step (2) of the process method, the concentration of concentrated sulfuric acid is 93%; ensuring the full reaction of concentrated sulfuric acid and materials in the leaching process.
Furthermore, in the step (2) of the process method, the acid content of the anolyte is 45 g/L-50 g/L.
Furthermore, in the step (2) of the process method, the pulping reaction time is 0.5-2 h, and the leaching reaction time is 1-4 h.
Furthermore, in the step (2) of the process method, the reaction temperature of the pulping reaction and the leaching reaction is between 45 ℃ and 60 ℃.
Further, in the step (2) of the process method, the generated hydrogen sulfide gas is absorbed by a two-stage absorption tower; in the pulping and leaching process, a certain amount of hydrogen sulfide gas is generated, and at the moment, part of the hydrogen sulfide gas is absorbed by using a two-stage absorption tower.
The technological principle of the process method for producing electrolytic manganese metal by utilizing silicomanganese slag is as follows:
the manganese-silicon slag is high-temperature slag discharged when manganese ore, coke, silica and other raw materials are used by enterprises for smelting manganese-silicon alloy in a reducing atmosphere in an ore furnace, the high-temperature molten manganese-silicon alloy slag is quenched by water or naturally cooled in the air to form granular or compact massive glass-phase silicate with a loose structure, and the main chemical component of the manganese-silicon slag is SiO 2 And CaO, followed by MnO, mn, mnS, al 2 O 3 And MgO, caS. The process method comprises the steps of utilizing manganese in manganese silicon slag to exist in a positive 2 valence state or a simple substance, using anode liquor to carry out acid leaching to control the manganese in the slag to be below 2%, leaching and recycling the manganese to prepare manganese sulfate electrolyte for electrolytic manganese production. The specific reaction process is shown below.
MnO+H 2 SO 4 ==MnSO 4 +H 2 O
Mn+H 2 SO 4 ==MnSO 4 +H 2 ↑
CaS+H 2 SO 4 ==CaSO 4 +H 2 S↑
MnS+H 2 SO 4 ==MnSO 4 +H 2 S↑
The process method for producing electrolytic manganese metal by utilizing silicomanganese slag has the beneficial effects that:
(1) The silicon-manganese slag or the silicon-manganese slag and the anode slag are mixed according to a certain proportion, then the anode liquid and concentrated sulfuric acid generated in the electrolytic manganese production process are utilized to carry out pulping and leaching, and then the anode liquid and manganese ore are used for preparing neutral liquid and the metal manganese is recovered through electrolysis, so that the industrial solid waste silicon-manganese slag generated in the silicon-manganese alloy production process can be recycled; meanwhile, anode slag generated in the manganese electrolysis process is effectively utilized, hydrogen sulfide gas generated in the pulping and leaching process is effectively removed, resource waste is reduced, and environmental pollution is reduced;
(2) By adjusting the control parameters such as the proportion of anode slag and silicomanganese slag, the reaction temperature of pulping, the acid concentration of anolyte and the like, on the basis of ensuring that the manganese content of slag (the total manganese content in external slag discharge) is less than or equal to 2.0 percent and the tetravalent manganese is less than or equal to 0.5 percent, a large amount of anode slag is consumed;
(3) Through the control parameters of the proportion of the silicomanganese slag and the concentrated sulfuric acid, the leaching reaction temperature and the leaching reaction time, the concentration of the residual acid after leaching and the like, on the basis of ensuring that the manganese content of the slag (the total manganese content in the external slag discharge) is less than or equal to 1.0 percent, a large amount of silicomanganese slag is consumed;
(4) The manganese element in the silicomanganese slag is recovered, the manganese processing industry chain is extended, a new market is developed while the environment is protected and the land is saved, the utilization way of the silicomanganese slag is widened, the manganese industry is developed healthily and orderly, and the national sustainable development road is more met.
Drawings
Fig. 1 and fig. 2 are schematic flow charts of the process method for producing electrolytic manganese metal by using silicomanganese slag according to the invention.
Detailed Description
Example 1
As shown in figure 1, the process method for producing electrolytic manganese metal by using silicomanganese slag comprises the following process steps.
(1) Preparing raw materials: the raw materials comprise silicomanganese slag, wherein the silicomanganese slag is generated in the processing process of silicomanganese, and the silicomanganese slag contains 6-8% of manganese and 3-5% of sulfides (including calcium sulfide, manganese sulfide, magnesium sulfide and the like) besides silicate, oxide and other substances; the silicomanganese slag is crushed into silicomanganese slag powder with the grain size less than 100 meshes by a roller press and used as raw material slag powder.
(2) Pulping and leaching: putting anolyte generated in the process of electrolyzing metal manganese into a chemical combination barrel, putting the raw material slag powder in the step (1) into the chemical combination barrel, and stirring to perform pulping reaction for 1 h; adding 93% concentrated sulfuric acid for leaching reaction for 2 h; in the process, the temperature of pulping reaction and leaching reaction is between 45 ℃ and 60 ℃, the acid content of anolyte is 45g/L to 50g/L, and the specific dosage of concentrated sulfuric acid is calculated and added according to the acid-mineral ratio of 0.85 to 0.95; in the process, sulfides in the silicomanganese slag react with sulfuric acid to generate hydrogen sulfide gas and sulfate, and the hydrogen sulfide gas is absorbed by the primary absorption tower and the secondary absorption tower in sequence, so that the aim of removing the hydrogen sulfide gas is fulfilled.
(3) Mixing with mineral powder: filter-pressing the materials after pulping and leaching, mixing the obtained filtrate with mineral powder to obtain a mixed solution, and sending the obtained filter residue into a slag yard for stockpiling; wherein the mineral powder is manganese carbonate mineral powder or manganese oxide mineral powder.
(4) Acid collection and impurity removal: adding baking powder into the mixed solution for acid recovery treatment, and adding ammonia water for neutralization reaction when the residual acid is reduced to below 2 g/L; when the pH value of the system reaches 6.7-7.2, adding hydrogen peroxide and introducing air simultaneously to remove iron ions in the system, and adding SDD to remove heavy metals in the system, thereby removing impurities in the mixed solution.
(5) Purification: performing filter pressing on the material obtained in the step (4), adding a flocculating agent (aluminum sulfate and/or polyacrylamide) and activated carbon into the obtained filtrate, stirring, standing for 4-5 hours, condensing micro particles in the system, and adsorbing micromolecular organic matters, colloidal substances and the like; then, carrying out filter pressing on the upper layer liquid after standing again to obtain filtrate; in the process, all generated filter residues are sent to a slag yard for stockpiling.
(6) Electrolysis: and (4) feeding the filtrate obtained in the step (5) as a neutral solution to an electrolytic manganese process for electrolysis to obtain metal manganese.
In addition, in the process, the consumption of the materials is that the silicomanganese slag and the mineral powder are mixed according to the mass ratio of 1 to 9, and the mixture of the silicomanganese slag and the mineral powder and the anolyte are mixed according to the mass ratio of 1 (12-15).
Example 2
As shown in figure 2, the process method for producing electrolytic manganese metal by using silicomanganese slag comprises the following process steps.
(1) Preparing raw materials: the raw materials comprise silicomanganese slag and anode slag; the silicomanganese slag is generated in the processing process of silicomanganese alloy, and contains 6-8% of manganese and 3-5% of sulfide (including calcium sulfide, manganese sulfide, magnesium sulfide and the like) besides silicate, oxide and the like; the anode slag is generated in the process of electrolyzing metal manganese, and the main component of the anode slag is manganese dioxide; crushing the silicomanganese slag into silicomanganese slag powder with the particle size of less than 100 meshes by using a roller press, drying the anode slag, crushing the anode slag into anode slag powder with the particle size of less than 100 meshes by using the roller press, and mixing the silicomanganese slag powder and the anode slag powder to be used as raw material slag powder.
(2) Pulping and leaching: putting anolyte generated in the process of electrolyzing metal manganese into a chemical combination barrel, putting the raw material slag powder in the step (1) into the chemical combination barrel, and stirring to perform pulping reaction for 1 hour; adding 93% concentrated sulfuric acid for leaching reaction for 2 h; wherein the acid content of the anolyte is 45 g/L-50 g/L, the specific dosage of concentrated sulfuric acid is calculated and added according to the acid-mineral ratio of 0.85-0.95, and the temperatures of pulping reaction and leaching reaction are both 45-60 ℃. In the process, sulfides in the silicomanganese slag react with sulfuric acid in advance to generate hydrogen sulfide gas and sulfate, and meanwhile, manganese dioxide in the anode slag is treated by sulfides under the condition that anolyte is used as a carrier, namely, the hydrogen sulfide gas is rapidly contacted with tetravalent manganese ions in the anode slag in the anolyte to generate an oxidation-reduction reaction, negative divalent sulfur is oxidized into elemental sulfur or low-valence sulfate by reducing the hydrogen sulfide, and tetravalent manganese is oxidized into divalent manganese (manganese sulfate) by oxidizing the tetravalent manganese; in the reaction process, the manganese content of the generated waste slag is below 1.5 percent, the tetravalent manganese content is below 0.4 percent, about 60 percent of all generated hydrogen sulfide gas is treated by anode slag, and the rest is absorbed and treated by two-stage absorption towers, so that the aim of removing the hydrogen sulfide gas is fulfilled.
(3) Mixing with mineral powder: filter-pressing the materials after pulping and leaching, mixing the obtained filtrate with mineral powder to obtain a mixed solution, and sending the obtained filter residue into a slag yard for stockpiling; wherein the mineral powder is manganese carbonate mineral powder or manganese oxide mineral powder.
(4) Acid collection and impurity removal: adding baking powder into the mixed solution for acid recovery treatment, and adding ammonia water for neutralization reaction when the residual acid is reduced to below 2 g/L; when the pH value of the system reaches 6.7-7.2, adding hydrogen peroxide and introducing air simultaneously to remove iron ions in the system, and adding SDD (sodium dimethyl dithiocarbamate) to remove heavy metals in the system, thereby removing various impurities in the mixed solution.
(5) Purification: performing filter pressing on the material obtained in the step (4), adding a flocculating agent (aluminum sulfate and/or polyacrylamide) and active carbon into the obtained filtrate, stirring, standing for 4-5 hours, condensing micro particles in the system, and adsorbing micro-molecular organic matters, colloidal substances and the like; then, carrying out filter pressing on the upper layer liquid after standing again to obtain filtrate; in the process, all generated filter residues are sent to a slag yard for storage.
(6) Electrolysis: and (5) taking the filtrate obtained in the step (5) as a neutral solution, and sending the neutral solution to an electrolytic manganese process for electrolysis to obtain the metal manganese.
In addition, in the process, the anode slag and the silicomanganese slag are mixed according to the mass ratio of 1.
Example 3
The neutral solution prepared in the embodiment 1 and the embodiment 2, namely the filtrate in the step (5), has the performance parameters of 38-43 g/L of manganese content and 80-86 g/L of ammonium sulfate content; the manganese content of the discharged filter residue generated in the whole process is 1.34-1.89%, the total recovery rate of manganese in the silicomanganese residue is over 75%, and the yield of the electrolytic single plate is 3.42-3.68 kg, which is the same as that of the traditional electrolytic single plate.
In the embodiment 1, the absorption rate of hydrogen sulfide gas absorbed by the secondary absorption tower is more than 95%, the content of hydrogen sulfide in the discharged gas is less than 8mol/mol, and the external discharge capacity of ammonia gas is less than 20mol/mol; in the embodiment 2, the recovery rate of absorbing hydrogen sulfide gas by using anode slag is 60%, and the secondary absorption tower is combined to absorb the residual hydrogen sulfide gas, so that the content of hydrogen sulfide in the exhaust gas is less than 8mol/mol, and the external discharge capacity of ammonia gas is less than 20mol/mol.
In addition, in the whole process, the parameters of ammonia consumption, impurity removal SDD consumption, electrolysis power consumption, current efficiency and the like are basically not different from the existing electrolytic manganese production process.
In conclusion, the silicon-manganese slag is used as a main raw material, the anode slag is utilized, the hydrogen sulfide gas can be effectively treated under the condition that the anode liquid is used as a carrier, meanwhile, the manganese content in the external slag discharge meets the emission requirement, the total manganese recovery rate is high, the energy and resources are saved, the environmental pollution is reduced, and the green, environment-friendly and sustainable development of the manganese processing industry is realized.
Claims (9)
1. A process method for producing electrolytic manganese metal by utilizing silicomanganese slag is characterized by comprising the following process steps:
(1) Preparing raw materials: the raw material comprises silicomanganese slag; crushing silicomanganese slag generated in the processing process of silicomanganese alloy into silicomanganese slag powder, and using the silicomanganese slag powder as raw material slag powder; the raw material also comprises anode slag; drying and crushing anode slag generated in the process of electrolyzing metal manganese into anode slag powder, and mixing silicon manganese slag powder and anode slag powder to be used as raw material slag powder;
(2) Pulping and leaching: mixing and stirring raw material slag powder and anolyte generated in the process of electrolyzing metal manganese, carrying out pulping reaction, and then adding concentrated sulfuric acid for leaching reaction;
(3) Mixing with mineral powder: performing filter pressing on the materials after pulping and leaching, and mixing the obtained filtrate with mineral powder to obtain a mixed solution; wherein the mineral powder is manganese carbonate mineral powder or manganese oxide mineral powder;
(4) Acid collection and impurity removal: adding baking powder into the mixed solution for acid recovery treatment, and adding ammonia water for neutralization reaction when the residual acid is reduced to below 2 g/L; when the pH value of the system reaches 6.7-7.2, adding hydrogen peroxide and introducing air simultaneously to remove iron ions in the system, and adding SDD to remove heavy metals in the system;
(5) Purifying: performing filter pressing on the material obtained in the step (4), adding a flocculating agent and active carbon into the obtained filtrate, stirring, standing for a certain time, and performing filter pressing on the upper layer liquid again to obtain a filtrate;
(6) Electrolysis: and (4) feeding the filtrate obtained in the step (5) as a neutral solution to an electrolytic manganese process for electrolysis to obtain metal manganese.
2. The process method as claimed in claim 1, wherein in the step (1), the silicomanganese slag is crushed into silicomanganese slag powder with the particle size of less than 100 meshes by using a roller press, and the anode slag is dried and then crushed into anode slag powder with the particle size of less than 100 meshes by using the roller press.
3. The process method as claimed in claim 1, wherein the anode slag and the silicomanganese slag are mixed according to the mass ratio of 1 (8-10).
4. The process method according to claim 1, wherein the mass ratio of the raw material slag powder to the mineral powder is as follows: the mineral powder is 2.
5. The process method according to claim 1, wherein the mass ratio of the raw material slag powder, the mineral powder and the anolyte is (raw material slag powder + mineral powder): the anolyte is 1 (10-15).
6. The process method of claim 1, wherein in the step (2), the concentration of the concentrated sulfuric acid is 93%, and the acid content of the anolyte is 45g/L to 50g/L.
7. The process method as claimed in claim 1, wherein in the step (2), the pulping reaction time is 0.5-2 h, and the leaching reaction time is 1-4 h.
8. The process of claim 1, wherein in step (2), the reaction temperature for both the pulping reaction and the leaching reaction is between 45 ℃ and 60 ℃.
9. The process of claim 1, wherein in step (2), the hydrogen sulfide gas produced is subjected to an absorption treatment by means of a two-stage absorption tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772841.4A CN113463134B (en) | 2021-07-08 | 2021-07-08 | Process method for producing electrolytic manganese metal by using silicomanganese slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772841.4A CN113463134B (en) | 2021-07-08 | 2021-07-08 | Process method for producing electrolytic manganese metal by using silicomanganese slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113463134A CN113463134A (en) | 2021-10-01 |
| CN113463134B true CN113463134B (en) | 2023-01-13 |
Family
ID=77879195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110772841.4A Active CN113463134B (en) | 2021-07-08 | 2021-07-08 | Process method for producing electrolytic manganese metal by using silicomanganese slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113463134B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481218A (en) * | 2021-12-22 | 2022-05-13 | 四川中哲新材料科技有限公司 | Method for deeply purifying manganese sulfate solution in electrolytic manganese metal production |
| CN114250488A (en) * | 2021-12-31 | 2022-03-29 | 宁夏天元锰材料研究院(有限公司) | Method for producing manganese sulfate electrolyte |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA77323C2 (en) * | 2005-01-20 | 2006-11-15 | Volodymyr Yakovych Kapelianov | Process for manganese preparation of the slug of silicomanganese production |
| CN101748447B (en) * | 2009-11-30 | 2011-09-21 | 中信锦州铁合金股份有限公司 | Method for producing electrolytic manganese metal |
| CN102174705B (en) * | 2011-03-10 | 2012-12-12 | 中信锦州金属股份有限公司 | Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron |
| CN102140650B (en) * | 2011-03-10 | 2013-10-16 | 中信锦州金属股份有限公司 | Method and application for producing electrolytic manganese by using novel oxidizing agent for removing iron |
-
2021
- 2021-07-08 CN CN202110772841.4A patent/CN113463134B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113463134A (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100355485C (en) | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent | |
| CN109928414B (en) | Method for synchronously preparing calcium aluminate steelmaking desulfurizer by removing impurities through aluminum ash sintering | |
| CN113463134B (en) | Process method for producing electrolytic manganese metal by using silicomanganese slag | |
| AU2020100054A4 (en) | A combined process for the recovery of valuable metals from waste ternary cathode materials based on chlorination roasting at medium temperature and water leaching | |
| CN109928413B (en) | Method for synchronously preparing sodium aluminate by sintering and denitrifying aluminum ash with soda | |
| CN110436600B (en) | Method for producing titanium-rich slag and water purifying agent by jointly treating red mud and iron-containing waste acid | |
| CN110106312B (en) | Process for producing LF (ladle furnace) slagging agent by using electrolytic aluminum carbon slag | |
| CN111485063B (en) | High-efficiency utilization process of aluminum ash in electrolytic aluminum plant | |
| CN110093471B (en) | Efficient and low-consumption comprehensive utilization method of red mud | |
| CN109650345A (en) | Method for respectively utilizing sulfur and calcium resources in gypsum | |
| CN113637840A (en) | Method for recovering zinc from zinc ferrite resource by using calcification ball-milling roasting-alkaline leaching method | |
| CN113857222A (en) | Harmless treatment method for red mud | |
| CN110172538B (en) | Efficient red mud resource utilization system and process | |
| CN113751476B (en) | Method for cooperative treatment and cyclic utilization of metallurgical solid waste and municipal waste incineration fly ash | |
| CN106698887B (en) | A kind of preparation method and its application method of composite inorganic flocculant poly aluminium sulfate iron | |
| CN111003775A (en) | Method for treating arsenic in waste acid by copper slag and carbide slag | |
| CN111039299B (en) | Method for efficiently recycling lead-zinc tailings | |
| CN102634656B (en) | Method for preparing electrolytic manganese/electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium | |
| CN110282885B (en) | Red mud step-by-step treatment and comprehensive utilization production system and process | |
| CN114888036B (en) | Method for cooperatively recycling aluminum electrolysis overhaul slag and mining and metallurgy slag | |
| AU2021104221A4 (en) | Method for improving desulfurization efficiency of electrolytic manganese ore/slag slurry | |
| CN214270947U (en) | System for harmless, resourceful processing of aluminium industry waste cathode carbon piece | |
| CN113830776A (en) | Method for recovering polymetallic crystal co-production water glass from copper-nickel sulfide ore tailings | |
| CN114934153B (en) | Method for producing HRB400 efficient desulfurizing agent and extracting lithium by using carbon slag and aluminum ash | |
| CN116177917B (en) | Electrolytic manganese slag treatment method and active micro powder material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |