阅读说明：本技术 用氧化锰矿石生产炉料的方法及其应用 (Method for producing furnace charge by using manganese oxide ore and application thereof ) 是由 庞炼红 唐诗祝 张雪莲 庞列培 于 2018-09-27 设计创作，主要内容包括：本发明涉及用氧化锰矿石生产炉料的方法,包括以下步骤：将氧化锰矿石破碎、磨成粉后浆化,然后鼓入二氧化硫气体搅拌浸出或加入亚硫酸铵溶液,再加入浓硫酸搅拌浸出,再调节pH至6.0-6.4,除杂、压滤后固液分离得到硫酸锰溶液和压滤块A；B.硫酸锰溶液静置后分离上清液和沉淀,将沉淀压滤,压滤块A加入步骤A的浆化工序；上清液于38-42℃温度下加入碱搅拌调节pH至8.5-9,将得到的沉淀压滤后固液分离,得到氢氧化锰压滤块B和硫酸铵溶液,调节硫酸铵溶液的pH至11-12,压滤,得到氢氧化镁压滤块和压滤液；C.将氢氧化锰压滤块B水洗后压滤,得到氢氧化锰压滤块C；氢氧化锰压滤块C烧结得到炉料。该方法能够有效除去锰矿中的有害杂质,富集锰元素,提高了选矿效率。(The invention relates to a method for producing furnace charge by using manganese oxide ore, which comprises the following steps: crushing manganese oxide ores, grinding into powder, pulping, blowing sulfur dioxide gas, stirring and leaching or adding an ammonium sulfite solution, adding concentrated sulfuric acid, stirring and leaching, adjusting the pH to 6.0-6.4, removing impurities, performing filter pressing, and performing solid-liquid separation to obtain a manganese sulfate solution and a filter pressing block A; B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block A into the slurrying process in the step A; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution; C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge. The method can effectively remove harmful impurities in the manganese ore, enrich manganese elements and improve the ore dressing efficiency.)

1. The method for producing the furnace charge by using the manganese oxide ore is characterized by comprising the following steps of:

A. crushing manganese oxide ores, grinding into powder, pulping, blowing sulfur dioxide gas, stirring and leaching or adding an ammonium sulfite solution, adding concentrated sulfuric acid, stirring and leaching, adjusting the pH to 6.0-6.4, removing impurities, performing filter pressing, and performing solid-liquid separation to obtain a manganese sulfate solution and a filter pressing block A;

B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block A into the slurrying process in the step A; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;

C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge.

2. The method according to claim 1, wherein the slurrying degree in the step A is 25-40g/L of divalent manganese ion content in the solution after slurrying.

3. A method according to claim 1 or 2, characterized in that the amount of sulphur dioxide is 1-1.3 times the sum of the amounts of all the metallic elements in the ore, the amount of ammonium sulphite solution is 1-1.3 times the sum of the amounts of all the metallic elements in the ore with ammonium sulphite contained in the solution, and the amount of concentrated sulphuric acid is 1-1.3 times the sum of the amounts of all the metallic elements in the ore with sulphuric acid contained in the solution.

4. The method according to claim 1, 2 or 3, wherein in step A, the stirring linear velocity is 20-30 m/s.

5. The method of claim 1, 2, 3 or 4, wherein the base in step B is an aqueous ammonia solution and the stirring linear velocity is 20-30 m/s.

6. The method of claim 1, 2, 3, 4 or 5, further comprising the steps of: and step A, recovering acid mist and reaction tail gas generated after the reaction of the blown sulfur dioxide gas in a slurrying tank.

7. The method of claim 1, 2, 3, 4, 5 or 6, further comprising the steps of: and C, adding the washing water obtained in the step C into an ammonium sulfate solution, stirring and adding quicklime at the temperature of less than or equal to 90 ℃, recovering the generated ammonia gas with water to obtain an ammonia water solution, carrying out filter pressing on the solution after reaction, carrying out solid-liquid separation to obtain a calcium sulfate filter pressing block and water, and standing the water for impurity removal and then recycling.

8. The method of claim 7, further comprising the steps of: and washing the filter pressing block A with water, then carrying out filter pressing to obtain a filter pressing block and a solution, homogenizing the filter pressing block and the calcium sulfate filter pressing block, adjusting the content of calcium, magnesium, silicon, aluminum and iron in the mixture according to production requirements, homogenizing, adding coal powder, and calcining to obtain the cement additive.

9. Use of the charge produced by the process of any one of claims 1 to 8, , in the production of manganese alloys.

Technical Field

The invention belongs to the technical field of ore pretreatment by using agglomeration, briquetting, bonding and granulation methods, and particularly relates to a method for producing furnace burden by using manganese oxide ore.

Background

At present, the beneficiation methods are divided into two types, namely physical beneficiation and chemical beneficiation, wherein the physical beneficiation comprises a magnetic separation method, a gravity separation method, an electrostatic separation method, a friction beneficiation method, a particle size beneficiation method, a shape beneficiation method, a beneficiation method and the like, and the chemical beneficiation comprises a flotation method, a roasting method, a leaching method and the like. However, the method generally has the defects of poor ore dressing effect on manganese ores, limited manganese enrichment and harmful impurity removal effect, unobvious phosphorus removal effect, great environmental pollution, low manganese recovery rate, large amount of waste residues and high cost. The leaching rule is good in manganese-rich phosphorus removal and impurity removal effects, but the consumption of auxiliary materials such as acid and ammonia water is large, and the cost is high.

Manganese oxide ore is mainly composed of manganese durite (the main component is mMnO. MnO)₂·H₂O), pyrolusite (MnO as main component)₂) Manganese bioxide (Mn as the main component)₂O₂·H₂O), permanganic acid ore (MnO as main component)₂·H₂O), brown manganese ore (Mn as main component)₂O₃) And black manganese ore (Mn as the main component)₃O₄) And square manganese ore (MnO as main component), and the like, wherein the gangue is mainly silicate mineral, and also carbonate mineral mercury mineral powder dryer substances are usually accompanied with pig iron, phosphorus, nickel, cobalt and other components.

The manganese content of manganese oxide ores in China is low and is about 7-15%, and along with the fact that high-quality manganese-rich ore resources are increasingly deficient, imported high-quality ores such as Australian ores and the like must be imported to supplement the manganese ore resources in China, so that the processing cost of manganese ores and manganese in China is higher and smaller, and the profit margin is smaller and smaller. At present, the beneficiation method of manganese oxide ore in China is mainly a gravity separation method. However, the manganese content in manganese oxide ores in China is low, so that the beneficiation effect is not ideal, the enrichment degree of manganese is not high, and the content of harmful impurities such as phosphorus elements in the selected ores is high.

Disclosure of Invention

In view of the above, the present invention provides methods for producing burden using manganese oxide ore.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for producing a charge from manganese oxide ore, comprising the steps of:

A. crushing manganese oxide ores, grinding into powder, pulping, blowing sulfur dioxide gas, stirring and leaching or adding an ammonium sulfite solution, adding concentrated sulfuric acid, stirring and leaching, adjusting the pH to 6.0-6.4, removing impurities, performing filter pressing, and performing solid-liquid separation to obtain a manganese sulfate solution and a filter pressing block A;

B. standing the manganese sulfate solution, separating supernatant and precipitate, carrying out filter pressing on the precipitate, and adding a filter pressing block A into the slurrying process in the step A; adding alkali into the supernatant at the temperature of 38-42 ℃, stirring and adjusting the pH to 8.5-9, performing solid-liquid separation on the obtained precipitate after filter pressing to obtain a manganese hydroxide filter pressing block B and an ammonium sulfate solution, adjusting the pH of the ammonium sulfate solution to 11-12, and performing filter pressing to obtain a magnesium hydroxide filter pressing block and a filter pressing solution;

C. washing the manganese hydroxide filter pressing block B with water and then carrying out filter pressing to obtain a manganese hydroxide filter pressing block C; and sintering the manganese hydroxide filter pressing block C to obtain furnace charge.

The furnace burden can also be produced according to the method by using the fly ash generated in the production process of the roasted ore of manganese carbonate ore and the manganese alloy.

The slurrying refers to mixing the ore with water.

The method can effectively remove harmful impurities (such as phosphorus, sulfur and the like) in the manganese ore, enriches the manganese element, enables the manganese element to become furnace burden for producing manganese alloy, improves the ore dressing efficiency, reduces the production cost and avoids environmental pollution.

And step , grinding in step A to powder with 80-100 meshes.

And step , the slurrying degree in the step A is that the content of the divalent manganese ions in the slurried solution is 25-40 g/L.

And , using sulfur dioxide 1-1.3 times of the sum of all the metal elements in the ore, using ammonium sulfite solution 1-1.3 times of the sum of all the metal elements in the ore, and using concentrated sulfuric acid 1-1.3 times of the sum of all the metal elements in the ore.

And step , the alkali in the step B is ammonia water solution, and the stirring linear speed is 20-30 m/s.

Step , the sintering temperature in step C is 1400-1700 ℃.

, recovering the acid mist and tail gas generated by the reaction of the blown sulfur dioxide gas in the step A.

The method treats the gas generated in the reaction process, avoids the pollution to the environment and improves the resource utilization rate.

And , adding the washing water obtained in the step C into an ammonium sulfate solution, slowly adding quicklime under stirring at the temperature of less than or equal to 90 ℃, recovering the generated ammonia gas with water to obtain an ammonia water solution, performing pressure filtration on the solution after reaction, performing solid-liquid separation to obtain a calcium sulfate filter cake and water, standing the water, removing impurities, and recycling.

And , stirring at a linear speed of 10-20 m/s.

The method recovers ammonia water produced by electrolyzing metal manganese by using calcium oxide, produces an ammonia water solution, solves the source problem of ammonia water and calcium sulfate, does not need to purchase calcium sulfate, and solves the transportation problem of hazardous chemical products such as ammonia water, liquid ammonia and the like.

, the method also includes the step of using the obtained ammonia solution to adjust the pH value of the solution.

And , adding calcium lime in the amount to complete the ammonium sulfate reaction.

, washing the filter pressing block A, filter pressing to obtain filter pressing block and solution, homogenizing the filter pressing block and the calcium sulfate filter pressing block, regulating the content of calcium, magnesium, silicon, aluminum and iron in the mixture according to production requirements, homogenizing, adding coal powder, and calcining to obtain the cement additive.

, separating the powder and gas generated during calcining, adding the powder into rotary furnace for cyclic calcining, using the gas sulfur dioxide to prepare sulfuric acid, recovering the tail gas from sulfuric acid preparation with calcium hydroxide or manganese dioxide, and using the recovered mixture as cement additive or manganese preparing material.

The method recovers high-value elements such as sulfur, nitrogen, manganese and the like in the slag, and uses silicon, iron, calcium and aluminum in the slag for producing cement additives or manganese-making raw materials, thereby changing waste into valuable, reducing pollution and realizing the recovery and reutilization of resources.

The method produces cement additive or manganese raw material while processing waste residue, so that ammonium sulfate and sulfuric acid are recycled, and production cost is reduced.

And , calcining at a temperature of more than or equal to 1200 ℃ and less than 1450 ℃.

, further comprising the following steps of washing the filter pressing block A with water, standing, cooling, removing the precipitate to obtain supernatant, adjusting the pH to 9-10, standing, filter-pressing, performing solid-liquid separation, wherein the filter pressing block is used for the slurrying process in the step A, and the solution is adjusted to pH 6.5-7.5 and is used as water for washing slag for recycling.

The method recycles ammonium sulfate and water, and reduces production cost while treating waste residues.

The invention also aims to protect the application of the furnace burden prepared by the method in the preparation of manganese alloy.

The furnace burden prepared by the method is used for producing manganese alloy, no water quenching slag is generated, so that the loss of manganese caused by taking manganese away from water quenching slag is avoided, and the recovery rate of manganese is improved.

The invention has the beneficial effects that:

(1) the method can effectively remove harmful impurities (such as phosphorus, sulfur and the like) in the manganese ore, enriches the manganese element, enables the manganese element to become furnace burden for producing manganese alloy, improves the ore dressing efficiency, reduces the production cost and avoids environmental pollution.

(2) The method produces cement additive or manganese raw material while treating waste residue, and reduces production cost.

(3) The method recycles ammonium sulfate, sulfuric acid and water, and reduces production cost while treating waste residues.

(4) The method uses calcium oxide to recover ammonia water produced by electrolyzing metal manganese, produces ammonia water solution, solves the problem of sources of ammonia water and calcium sulfate, and solves the problem of transportation of hazardous chemical products such as ammonia water and liquid ammonia.

(5) According to the method, about 1 ton of furnace charge for producing high-carbon ferromanganese or silicon-manganese alloy and 6.7 to 6.9 tons of cement additive can be prepared when consuming 700 or 1600 ℃ of electricity per 6.9 to 7.0 tons of manganese oxide ore with 9.86 to 10.27 percent of manganese content, 1.75 to 1.77 percent of phosphorus content and 2 to 2.5 percent of sulfur content. The obtained furnace charge contains 65.37-65.62% of manganese element, 0.069-0.07% of phosphorus element and 0.01% of sulfur element.

Detailed Description

The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.