Process method for producing electrolytic manganese metal by using silicomanganese slag

文档序号：63139 发布日期：2021-10-01 浏览：42次中文

阅读说明：本技术 一种利用硅锰渣生产电解金属锰的工艺方法 (Process method for producing electrolytic manganese metal by using silicomanganese slag ) 是由贾天将段锋宋正平张志华虎大勇马林陈建红张国举马鹏飞李凯于 2021-07-08 设计创作，主要内容包括：本发明属于锰加工技术领域,涉及一种利用硅锰渣生产电解金属锰的工艺方法。该工艺方法,包括1.原料准备：将硅锰渣破碎为硅锰渣粉；2.制浆浸取：与阳极液进行制浆,加入浓硫酸进行浸取；3.与矿粉混合：压滤,将滤液与矿粉混合；4.收酸、除杂：加入焙烧粉进行收酸,加入氨水进行中和,加入双氧水并通入空气,去除铁离子,加入SDD去除重金属；5.净化：压滤,在滤液中加入絮凝剂和活性炭,静置、压滤；6.电解：获得金属锰。该工艺方法,使硅锰合金生产过程中产生的工业固废硅锰渣得以重新回收利用,减少资源浪费、减少环境污染,保护环境、节约土地,延伸锰加工产业链,拓宽硅锰渣的利用途径。(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 the utilization path of silicomanganese slag.)

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;

(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 (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.

2. The process of claim 1, wherein in step (1), the feedstock further 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.

3. The process method as claimed in claim 2, 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.

4. The process method of claim 2, wherein the anode slag and the silicomanganese slag are mixed according to the mass ratio of 1 (8-10).

5. The process method according to claim 1 or 2, wherein the mass ratio of the raw material slag powder to the mineral powder is as follows: the ratio of the mineral powder is 2:8 or 1: 9.

6. The process according to claim 1 or 2, wherein the mass ratio of raw material slag powder, mineral powder and anolyte is (raw material slag powder + mineral powder): the anolyte is 1 (10-15).

7. The process according to claim 1 or 2, wherein in the step (2), the concentrated sulfuric acid has a concentration of 93%, and the acid content of the anolyte is 45g/L to 50 g/L.

8. The process according to claim 1 or 2, wherein in the step (2), the time of the pulping reaction is 0.5 h-2 h, and the time of the leaching reaction is 1 h-4 h.

9. A process according to claim 1 or claim 2, wherein in step (2) the reaction temperature for both the pulping reaction and the leaching reaction is between 45 ℃ and 60 ℃.

10. The process according to claim 1 or 2, wherein in the step (2), the produced hydrogen sulfide gas is subjected to an absorption treatment by a two-stage absorption tower.

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 per 1 ton of silicomanganese produced, and therefore, the accumulated amount of the silicomanganese slag reaches hundreds of millions of tons according to the calculation that more than 1000 million tons of silicomanganese are generated in 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 the metallurgical industry; in addition, the silicomanganese slag contains various recyclable element components, and long-term storage is also a 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:

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 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 ratio of the mineral powder is 2:8 or 1: 9.

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 time of pulping reaction is 0.5-2 h, and the time of leaching reaction 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; during the pulping and leaching process, a certain amount of hydrogen sulfide gas is generated, and at the moment, partial hydrogen sulfide gas is absorbed by using a two-stage absorption tower.

The technological principle of the technological 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-smelting 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 SiO₂And CaO followed by MnO, Mn, MnS, Al₂O₃And MgO, CaS. The process methodThe method comprises the steps of utilizing manganese in manganese silicon slag to exist in a positive 2 valence state or a simple substance, using anolyte to leach, controlling the manganese in the slag to be below 2%, leaching and recycling the manganese to prepare a manganese sulfate electrolyte and using the manganese sulfate electrolyte for electrolytic manganese production. The specific reaction process is shown below.

MnO+H₂SO₄==MnSO₄+H₂O

Mn+H₂SO₄==MnSO₄+H₂↑

CaS+H₂SO₄==CaSO₄+H₂S↑

MnS+H₂SO₄==MnSO₄+H₂S↑

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) the silicon-manganese slag is largely consumed on the basis of ensuring that the manganese (the total manganese content in the external slag discharge) of the slag is less than or equal to 1.0 percent through the control parameters of the proportion of the silicon-manganese slag and concentrated sulfuric acid, the leaching reaction temperature and the leaching reaction time, the concentration of the residual acid after leaching and the like;

(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 for producing electrolytic manganese metal by using silicomanganese slag according to the present 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 alloy, and the silicomanganese slag 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 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.

(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, so that impurities in the mixed solution are removed.

(5) Purifying: 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 (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 consumption of the materials is that the silicomanganese slag and the mineral powder are mixed according to the mass ratio of 1:9, 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 silicomanganese slag into silicomanganese slag powder with the particle size smaller than 100 meshes by using a roller press, drying anode slag, crushing the anode slag into anode slag powder with the particle size smaller 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, the sulfide in the silicomanganese slag reacts with sulfuric acid in advance to generate hydrogen sulfide gas and sulfate, and meanwhile, the manganese dioxide in the anode slag is treated by the sulfide under the condition that anolyte is taken as a carrier, namely, the hydrogen sulfide gas quickly contacts 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 means of reducibility, and tetravalent manganese is reduced into divalent manganese (manganese sulfate) by means of oxidizability; 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.

(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.

In addition, in the process, the anode slag and the silicomanganese slag are proportioned according to the mass ratio of 1:9, the raw material slag powder consisting of the silicomanganese slag and the anode slag is proportioned with the mineral powder according to the mass ratio of 1:9, and the total amount of the raw material slag powder (including the silicomanganese slag and the anode slag) and the mineral powder is proportioned with the anode liquid according to the mass ratio of 1 (10-12).

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 20 mol/mol; in the embodiment 2, the recovery rate of absorbing hydrogen sulfide gas by anode slag is 60%, and the residual hydrogen sulfide gas is absorbed by combining a secondary absorption tower, so that 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 20 mol/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 recovery rate of manganese 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.

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Process method for producing electrolytic manganese metal by using silicomanganese slag

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