阅读说明：本技术 以碳酸锰矿石生产炉料的方法及其应用 (Method for producing furnace charge by manganese carbonate 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：本发明涉及以碳酸锰矿石生产炉料的方法,包括以下步骤：A.将碳酸锰矿石磨成粉后浆化,加酸搅拌浸出,然后调节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.将硫酸锰溶液静置后分离上清液和沉淀,将沉淀压滤,压滤块加入步骤A中与磨成粉的碳酸锰矿石共同进行浆化；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,降低了生产成本,杜绝了环境污染。(The invention relates to a method for producing burden by manganese carbonate ore, which comprises the following steps: A. grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing 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 into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; 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, improve the ore dressing efficiency, reduce the production cost and avoid environmental pollution.)

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

A. grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing 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 into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; 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 of claim 1, wherein the grinding in step a is grinding into 80-100 mesh powder.

3. The method according to claim 1 or 2, wherein the slurrying in step a is carried out to such an extent that the divalent manganese ion content in the slurried solution is 25-40 g/L.

4. The method according to claim 1, 2 or 3, wherein in the step A, the temperature of the solution after slurrying is kept at 50-80 ℃ during the acid adding process, the acid is concentrated sulfuric acid, the adding amount is 50-75g/L of sulfuric acid in the solution after adding, and the stirring linear speed during adding 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 as claimed in claim 1, 2, 3, 4 or 5, wherein the sintering temperature in step C is 1400-1700 ℃.

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 carbonate ore and application thereof.

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.

The manganese content of manganese carbonate ore in China is low, 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 ore and the like must be imported to make up for the supplement of manganese ore resources in China, so that the processing cost of manganese ore and manganese in China is higher and lower, and the profit margin is smaller and smaller. The manganese carbonate ores in China are mainly sedimentary manganese carbonate ores, main manganese ores of the sedimentary manganese carbonate ores are rhodochrosite, calciumdinite, manganese-containing calcite, ferromanganese ore and the like, gangue contains silicate and carbonate minerals, and is often accompanied by impurities such as sulfur, iron and the like, the components are relatively complex, the embedding particle size of the manganese ores is as small as several microns, the manganese ores are not easy to dissociate and are often difficult to obtain higher concentrate grade. At present, the mineral separation method of manganese carbonate ore comprises strong magnetic separation, dense medium mineral separation, flotation and the like. However, the manganese content in manganese carbonate 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 in the selected ores is high.

Disclosure of Invention

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

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

the method for producing furnace charge by manganese carbonate ore comprises the following steps:

grinding manganese carbonate ores into powder, pulping, adding acid, stirring and leaching, then adjusting the pH value to 6.0-6.4, removing impurities, and carrying out solid-liquid separation after filter pressing 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 into the step A to carry out slurrying together with the manganese carbonate ore which is ground into powder; 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.

In the scheme of the invention, the adjustment can be carried out according to different raw materials, if manganese oxide ore is contained in manganese carbonate ore, sulfur dioxide gas is introduced into the slurried solution, and the amount of the sulfur dioxide is 1-1.3 times of the amount of manganese substance contained in the manganese carbonate ore.

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), gangue is mainly silicate mineral, and carbonate ore mercury ore powder dryer is often accompanied with pig iron, phosphorus, nickel, cobalt and other components

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.

The grinding in the step A is to grind into 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.

The slurrying refers to mixing the ore with water.

And step , in the step A, keeping the temperature of the slurried solution at 50-60 ℃ in the acid adding process, wherein the acid is concentrated sulfuric acid, the adding amount of the acid is 50-75g/L of the concentration of sulfuric acid in the added solution, the stirring linear velocity is 20-30m/s in the adding process, and carbon dioxide generated by the reaction is recovered.

And step , stirring and leaching for 2.5-5 h.

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 ℃.

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 , adding quicklime for 2-3h, and recovering ammonia gas with water.

, 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 powder and gas generated during calcination, adding the powder into a rotary furnace for cyclic calcination, using the gas sulfur dioxide to produce sulfuric acid, and recovering the tail gas from sulfuric acid production with calcium hydroxide or manganese dioxide.

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 standing the solution obtained by washing the filter pressing block A with water, cooling, removing the precipitate to obtain supernatant, then adjusting the pH value to 9-10, standing, carrying out filter pressing and solid-liquid separation, wherein the filter pressing block is used for the slurrying process of the step A, the pH value of the solution is adjusted to 6.5-7.5, and the solution 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 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) When 6.8-7.0 tons of ore with 9.97-10.87% of manganese, 1.75-1.77% of phosphorus and 2-2.5% of sulfur is consumed by the method, about 1 ton of furnace charge for producing high-carbon ferromanganese or silicon-manganese alloy and 6.7-6.9 tons of cement additive can be prepared when 700 ℃ or 1600 ℃ of electricity is consumed. The obtained furnace charge contains 65.41-65.76% of manganese element, 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.