CN117468050A - An enhanced method for removing iron from iron-rich manganese ore leaching solution - Google Patents

An enhanced method for removing iron from iron-rich manganese ore leaching solution Download PDF

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CN117468050A
CN117468050A CN202311364235.4A CN202311364235A CN117468050A CN 117468050 A CN117468050 A CN 117468050A CN 202311364235 A CN202311364235 A CN 202311364235A CN 117468050 A CN117468050 A CN 117468050A
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iron
manganese
solution
slag
rich manganese
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舒建成
赵志胜
陈梦君
曾祥菲
邓宗瑜
杨勇
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

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  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for strengthening and removing iron in iron-rich manganese ore leaching liquid, and relates to the technical fields of electrolytic manganese leaching liquid purification and manganese slag source emission reduction. Solves the technical problems of poor manganese slag filtering property, serious manganese entrainment loss, high water content and the like of the iron-rich manganese ore leaching solution after iron removal in the prior art. The method adopts a method of neutralizing oxidation and seed crystal to promote aging to carry out reinforced removal on iron in the iron-rich manganese ore leaching solution. Compared with the traditional method, the method has the advantages that the iron removal rate is over 96-99%, the manganese loss is reduced by 10-15%, the generation of iron-manganese-rich slag is reduced by over 30%, and the manganese slag filtering speed is improved by over 80%. Compared with the prior art, the invention can reduce the water content and the slag yield of the iron-rich manganese slag, reduce the manganese entrainment loss and improve the filtering characteristic of the manganese slag while removing iron efficiently. In addition, the iron-removing slag can be used as seed crystal for recycling, and can also be used as raw materials for preparing products such as iron oxide red, and the like, and the filtrate can be purified to prepare qualified electrolytic manganese metal liquid.

Description

Reinforced removal method for iron in iron-rich manganese ore leaching solution
Technical Field
The invention relates to the technical field of electrolytic manganese leaching liquid purification and manganese slag source emission reduction, in particular to a method for strengthening and removing iron in iron-rich manganese ore leaching liquid.
Background
Electrolytic manganese metal is one of important basic substances and strategic resources in national economic development.
China is a large country of electrolytic manganese production, consumption and export, and along with the rapid development of electrolytic manganese industry and the increasing consumption of high-grade manganese ores, the grade of manganese ores is gradually reduced, and low-grade iron-rich manganese ores are gradually utilized.
Manganese ores are often associated with iron compounds, which also go into solution during the combined leaching process.
To obtain high quality electrolytic manganese metal products and high current efficiency, the leachate must be depleted of iron.
In addition, the manganese slag generated during iron removal has high water content (40% -50%), contains a large amount of iron oxides (25% -40%), manganese oxides (10% -20%), calcium sulfate (3% -5%), and magnesium sulfate (1% -3%), brings huge pressure to the environment, and also causes waste of resources.
Therefore, the removal of iron from the leachate has become one of the challenges to be resolved in the utilization of iron-rich manganese ores.
The related iron removal research of the manganese leaching solution at present mainly focuses on how to remove a small amount of iron in the solution, and related patents for removing iron in a high-concentration manganese, magnesium and iron system such as iron-rich manganese ore leaching solution are rarely related.
The conventional iron removal method adopts an oxidant to remove Fe under the condition of near neutrality (pH=6.5-7.0) 2+ Oxidation to Fe 3+ Adding a neutralizing agent to precipitate, and removing iron through solid-liquid separation.
For example, in patent CN201010578069.4, mnO is used 2 Fe is added to 2+ Oxidation, when determining Fe in solution 2+ And (3) after the concentration is reduced to below 1 mg/L, regulating the pH value of the solution to 6.4-7.0 by ammonia water, and then performing solid-liquid separation to remove iron.
The iron removal rate of the leachate treated by the method is more than 99 percent, but MnO is excessively added 2 The production cost is increased, part of manganese enters slag in the neutralization process, and the leaching solution after iron removal is filtered poorly.
And as in patent CN 202010938544.8, manganese dioxide in manganese ore is utilized to oxidize ferrous iron, and elemental manganese powder is utilized to neutralize and adjust pH, so that the aim of removing iron is achieved. However, the method has large slag yield, low manganese dioxide utilization rate of manganese ores and increased recycling and treatment difficulty of manganese slag.
In fact, most domestic electrolytic manganese metal manufacturers adopt a hydrolysis precipitation method to remove iron from leaching liquid, and usually adopt procedures of acid leaching of manganese ores, neutralization of residual acid, ferrous ion oxidation, iron ion hydrolysis precipitation and the like to produce the Fe (OH) in the same chemical combination reactor, and the process ensures that Fe (OH) generated by the hydrolysis precipitation is generated 3 The colloid particles are mixed with a large amount of acid leaching manganese slag, so that the solution filtering performance is poor, the subsequent solid-liquid separation is seriously influenced, the moisture content of filter residues is greatly increased, the adsorption and entrainment of moisture and valuable metals are increased, and the manganese slag has high moisture content and the waste of valuable metal resources are caused.
Fe (OH) formed in a subsequent process step by utilizing iron-containing impurities in manganese ores as in patent CN202011020606. X 3 The method can obtain the manganese sulfate solution meeting the electrolysis requirement by deeply purifying the vulcanized sulfuric acid solution, but the generated manganese slag is caused by Fe (OH) 3 The existence of colloid results in high water content and serious manganese loss.
Not only increases the production cost and interferes the normal operation of the production process, but also causes the waste of resources while jeopardizing the ecological environment.
In addition, a large amount of iron-manganese-rich slag generated by purifying and removing impurities of the leaching solution can only be simply piled up, and the recycling harmless treatment can not be performed.
Aiming at the difficult problem of iron removal in the iron-rich manganese ore leaching solution, the invention provides a method for strengthening and removing iron in the iron-rich manganese ore leaching solution, which not only can well strengthen and remove iron in the iron-rich manganese ore leaching solution, but also can reduce the water content of iron-rich manganese slag, reduce the manganese entrainment loss and improve the filtration characteristic of iron-rich manganese slag.
Disclosure of Invention
The invention aims to provide a method for strengthening and removing iron in iron-rich manganese ore leaching liquid, which solves the problems of high water content of iron-rich manganese slag, serious manganese entrainment loss, poor filtering characteristics and the like in the strengthening and removing process of iron in iron-rich manganese ore leaching liquid in the prior art.
The method can directly reduce the entrainment loss of manganese in the manganese slag, reduce the production amount of the manganese slag from the source when the iron-rich manganese ore is utilized for production, improve the filtration characteristic of the manganese slag, and is one of effective ways for realizing source emission reduction and pushing the application of the iron-rich manganese ore in the electrolytic manganese industry.
The technical effects that can be produced by the preferred technical scheme of the present invention are described in detail below.
In order to achieve the above purpose, the present invention provides the following technical solutions.
1. A method for strengthening and removing iron in iron-rich manganese ore leaching liquid is characterized in that a method for neutralizing, oxidizing and seed crystal promoting aging at a set temperature is adopted to strengthen and remove iron in the iron-rich manganese ore leaching liquid.
The method comprises the following steps.
S1, pumping the iron-rich manganese ore leaching solution into an iron-removing chemical combination barrel, blowing hot steam into the barrel body through an air pipe in the chemical combination barrel to enable the temperature of the solution to rise to a certain temperature, driving a stirring rod to stir through a motor during the process, and adding an alkaline agent through a dosing pipe to adjust the pH value of the solution.
And S2, introducing hot air into the solution, adding hydrogen peroxide by using a hydrogen peroxide adding pipe for reaction, and continuously adjusting the pH value of the solution.
And S3, adding seed crystals into the solution, adjusting the temperature and the pH of the solution, aging for a period of time, and performing filter pressing.
And S4, obtaining materials and solution after filter pressing.
2. The method for enhanced removal of iron from a ferro-manganese ore leachate according to claim 1, wherein the temperature in step S1 is 40-95 ℃, the alkaline agent is one or more of ammonia water, sodium carbonate, sodium hydroxide, etc., and the pH of the solution is adjusted to 2-6.
3. The method for strengthening and removing iron in the iron-rich manganese ore leaching solution according to claim 1, wherein the hot air inlet amount and the hydrogen peroxide adding amount in the step S2 are 1-2 times of reaction metering (based on the Fe component amount in the iron-rich manganese ore), the pH value of the solution is adjusted to 2-6, and the reaction time is 1-5 hours.
4. The method for strengthening and removing iron in the iron-rich manganese ore leaching solution according to claim 1, wherein the seed crystal in the step S3 is one or more of ferric oxide, iron powder, iron-rich manganese slag and roasting slag of the iron-rich manganese slag, the solid-liquid mass ratio of the seed crystal to the leaching solution is 1:1-1:10, and the aging time is 1-5 h.
5. The method for enhanced removal of iron from a ferro-manganese ore leachate according to claim 1, wherein the main component of the material in step S4 is Fe 2 O 3 And FeOOH can be further used as seed crystals for reuse in the iron removal process of the leaching solution or for resource utilization, and the filtrate can be used for preparing qualified electrolytic manganese metal liquid after purification and impurity removal.
Description of the embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
It will be apparent that the described embodiments are only some, but not all, embodiments of the invention.
All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The following examples will illustrate the invention in further detail in order to make the technical solutions, objects and advantages of the invention more apparent.
Example 1.
Taking 20L iron-rich manganese ore leaching solution in a chemical combination barrel, controlling the temperature, heating and stirring to enable the temperature inside the solution to be increased to 90 ℃, adjusting the pH value of the solution to 4 by using ammonia water, then adjusting the flow of a hydrogen peroxide adding pipeline, continuously adding hydrogen peroxide at the speed of 0.3L/h for oxidation, adjusting the pH value to be kept to 4 all the time by using ammonia water during the oxidation, adding 1 g/L iron-rich manganese slag serving as seed crystal for ageing 1 h after reacting 1 h, and performing filter pressing.
The iron removal rate is more than 99%, the manganese loss rate is 2%, and the slag yield is 19 g/L.
Compared with the manganese loss rate of the neutralization hydrolysis method adopted by enterprises, the method reduces the manganese loss rate by about 14 percent, reduces the generation of 64.45 percent of iron-rich manganese slag, and has the filtering characteristic of 0.0013 mL/(s cm) 2 ) Is increased to 0.1848 mL/(s.cm) 2 )。
Example 2.
Taking 20L iron-rich manganese ore leaching solution in a chemical combination barrel, controlling the temperature, heating and stirring to enable the temperature inside the solution to be increased to 90 ℃, adjusting the pH value of the solution to 4 by using ammonia water, then adjusting the flow of a hydrogen peroxide adding pipeline, continuously adding hydrogen peroxide at the speed of 0.3L/h for oxidation, adjusting the pH value to be kept to 4 all the time by using ammonia water during the oxidation, adding 5 g/L iron-rich manganese slag serving as seed crystal for ageing 1 h after reacting 1 h, and performing filter pressing.
The iron removal rate is about 98%, the manganese loss rate is about 12%, and the slag yield is 13 g/L.
Compared with the manganese loss rate of the neutralization hydrolysis method adopted by enterprises, the method reduces the manganese loss rate by about 4 percent, reduces the generation of 70 percent of iron-rich manganese slag, and has the filtering characteristic of 0.0013 mL/(s.cm) 2 ) Raised to 0.0253 mL/(s.cm) 2 )。
Example 3.
Taking 20L iron-rich manganese ore leaching solution in a chemical combination barrel, controlling the temperature, heating and stirring to enable the temperature inside the solution to be increased to 90 ℃, adjusting the pH value of the solution to 4 by using ammonia water, then adjusting the flow of a hydrogen peroxide adding pipeline, continuously adding hydrogen peroxide at the speed of 0.3L/h for oxidation, adjusting the pH value to be kept to 4 all the time by using ammonia water during the oxidation, adding 2 g/L iron-rich manganese slag serving as seed crystal for ageing 1 h after reacting 1 h, and performing filter pressing.
The iron removal rate was 91%, the manganese loss rate was 1%, and the slag yield was 17 g/L.
Compared with the manganese loss rate of the neutralization hydrolysis method adopted by enterprises, the method reduces the manganese loss rate by 15 percent, reduces the generation of 61 percent of iron-rich manganese slag, and has the filtering characteristic of 0.0013 mL/(s.cm) 2 ) Is increased to 0.1878 mL/(s.cm) 2 )。
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention.
Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1.一种富铁锰矿浸出液中铁的强化去除方法，其特征在于，采用设定温度下的中和、氧化、晶种促进陈化的方法对富铁锰矿浸出液中的铁进行强化去除。所述方法包括以下步骤。1. A method for enhanced removal of iron from the leachate of iron-rich manganese ore, which is characterized in that the iron in the leachate of iron-rich manganese ore is strengthened by using neutralization, oxidation, and crystal seed-promoted aging at a set temperature. The method includes the following steps. 2.S1:将富铁锰矿浸出液打入除铁化合桶中，通过化合桶中的空气管将热蒸汽鼓入桶体内部，使溶液温度升至一定温度，期间通过电机带动搅拌杆进行搅拌，并通过加药管加入碱性药剂调节溶液pH。2.S1: Pour the iron-rich manganese ore leaching solution into the iron-removing compound barrel, and blow hot steam into the barrel through the air pipe in the compound barrel to raise the temperature of the solution to a certain temperature. During this period, the motor drives the stirring rod for stirring. And add alkaline agent through the dosing tube to adjust the pH of the solution. 3.S2:向溶液中通入热空气并利用双氧水加入管添加双氧水进行反应，继续调节溶液pH。3.S2: Pour hot air into the solution and use the hydrogen peroxide adding tube to add hydrogen peroxide for reaction, and continue to adjust the pH of the solution. 4.S3:向溶液中添晶种，调节溶液温度及pH进行陈化，陈化一段时间后压滤。4.S3: Add crystal seeds to the solution, adjust the temperature and pH of the solution for aging, and then press filter after aging for a period of time. 5.S4:经压滤后，得到物料和溶液。5.S4: After pressure filtration, the material and solution are obtained. 6.根据权利要求1所述的一种富铁锰矿浸出液中铁的强化去除方法，其特征在于，步骤S1中所述的温度为40-95 ℃，碱性药剂可为氨水、碳酸钠、氢氧化钠等其中的一种或多种，调节溶液pH为2~6。6. The enhanced removal method of iron in the leaching solution of iron-rich manganese ore according to claim 1, characterized in that the temperature described in step S1 is 40-95°C, and the alkaline agent can be ammonia, sodium carbonate, hydroxide One or more of them, such as sodium, adjust the pH of the solution to 2~6. 7.根据权利要求1所述的一种富铁锰矿浸出液中铁的强化去除方法，其特征在于，步骤S2中所述的热空气通入量和双氧水添加量为反应计量的1~2倍率（以富铁锰矿石中Fe组分量为基础），调节溶液pH为2~6，反应时间为1~5 h。7. The enhanced removal method of iron in a kind of iron-rich manganese ore leaching solution according to claim 1, characterized in that the hot air input amount and hydrogen peroxide addition amount described in step S2 are 1 to 2 times the reaction measurement (based on (based on the amount of Fe component in iron-manganese-rich ore), adjust the pH of the solution to 2~6, and the reaction time is 1~5 h. 8.根据权利要求1所述的一种富铁锰矿浸出液中铁的强化去除方法，其特征在于，步骤S3中所述的晶种为氧化铁、铁粉、富铁锰渣、富铁锰渣焙烧渣的一种或多种，晶种与浸出液的固液质量比为1:1~1:10，陈化时间为1~5 h。8. The enhanced removal method of iron in the leaching solution of iron-rich manganese ore according to claim 1, characterized in that the seed crystal described in step S3 is iron oxide, iron powder, iron-rich manganese slag, and roasting of iron-rich manganese slag. One or more types of slag, the solid-liquid mass ratio of seed crystal and leachate is 1:1~1:10, and the aging time is 1~5 h. 9.根据权利要求1所述的一种富铁锰矿浸出液中铁的强化去除方法，其特征在于，步骤S4中所述的物料主要成分为Fe2O3及FeOOH，可进一步作为晶种回用于浸出液除铁过程或进行资源化利用，滤液净化除杂后可用于制备电解金属锰合格液。9. The enhanced removal method of iron in the leachate of iron-rich manganese ore according to claim 1, characterized in that the main components of the material described in step S4 are Fe 2 O 3 and FeOOH, which can be further used as seed crystals for recycling. The iron removal process of the leach solution may be used for resource utilization, and the filtrate can be used to prepare qualified electrolytic manganese metal liquid after purification and removal of impurities.
CN202311364235.4A 2023-10-20 2023-10-20 An enhanced method for removing iron from iron-rich manganese ore leaching solution Pending CN117468050A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118291679A (en) * 2024-03-26 2024-07-05 仙桃市中星电子材料有限公司 A method for treating iron-rich tailings produced by preparing titanium tetrachloride by ilmenite chlorination method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118291679A (en) * 2024-03-26 2024-07-05 仙桃市中星电子材料有限公司 A method for treating iron-rich tailings produced by preparing titanium tetrachloride by ilmenite chlorination method

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