阅读说明：本技术 一种用羟基组合液相还原处理氧化锰矿生产高纯硫酸锰的方法 (Method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore ) 是由 田世超 田凯元 于 2021-11-08 设计创作，主要内容包括：一种用羟基组合液相还原处理氧化锰矿生产高纯硫酸锰的方法,包括如下步骤：将硫酸锰液除铁、除去重金属离子后,浓缩至含锰≥120g/L,再进行1～2次的深度净化作业,然后再浓缩结晶,得到含锰≥99.5％的高纯度的七水硫酸锰MnSO-(4).7H-(2)0,继而气流烘干,得到99.5％的一水硫酸锰MnSO-(4).H-(2)O,母液返至予浓缩工序。所述深度净化是指在预浓缩后70～72℃的后液中加入NH-(4)F、NaF、HF或ALF-(3),使Ca,Mg生成溶解度很小的CaF-(2)、MgF-(2)沉淀,然后再经活性炭处理并精滤作业。(A method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore comprises the following steps: removing iron and heavy metal ions from the manganese sulfate liquid, concentrating until the manganese content is more than or equal to 120g/L, performing deep purification operation for 1-2 times, concentrating and crystallizing to obtain high-purity manganese sulfate heptahydrate MnSO with the manganese content of more than or equal to 99.5 percent 4 .7H 2 0, then drying by airflow to obtain 99.5 percent manganese sulfate monohydrate MnSO 4 .H 2 And O, returning the mother liquor to the pre-concentration process. The deep purification is to add NH into post-liquid at 70-72 ℃ after pre-concentration 4 F. NaF, HF or ALF 3 To form CaF with low solubility of Ca and Mg 2 、MgF 2 Precipitating, treating with active carbon, and fine filtering.)

1. A method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore is characterized by comprising the following steps:

(1) removing iron, acid and heavy metal ions from the crude manganese sulfate solution: injecting clean water into a reaction tank, adding manganese oxide ore containing 22% of manganese and manganese carbosulfate ore containing 20% of manganese, adding enzyme and a reducing aid, preheating the clean water to 70-72 ℃, reacting for 3.5-4.5 h at the reaction temperature of 90-93 ℃ after the addition of the materials, filtering, washing the slag once with the clean water to obtain filtrate and washing liquid, wherein the step of removing iron and reducing acid is to slowly flow industrial hydrogen peroxide and industrial ammonia water with the concentration of 1:1 into the washing liquid to ensure that the pH value of the liquid is 5.4 and keep the liquid unchanged for 25 minutes, and then, adding the following components: 0.6-0.9 kg/m sodium ferulate³Adding sodium ferbamate according to the proportion, stirring for 40 minutes after adding, sampling and analyzing whether Co and Ni are qualified or not, performing filter pressing to obtain qualified liquid and slag, taking the filtrate as deep purification liquid, taking the slag as a raw material for recovering Co and Ni,

(2) deep purification of filtrate: concentrating the filtrate of step (1) in a rising film concentratorMaintaining a vacuum degree of 510-620 mmHg and a vapor pressure of 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 70-72 ℃ until the manganese content is 120-140 g/L, and adding F according to the proportion of 1.0-1.4 times of the sum of CaO and MgO^-Reacting for 30-40 minutes, and then reacting according to the proportion of 3-8 kg/m³Adding active carbon to react for 30-40 minutes, standing for 1-2 hours according to the proportion of 0.03kg/m³Is added in a proportion of (NH)₄)₂S, reacting for 20-30 minutes, and standing for 24 hours;

(3) fine filtering the supernatant obtained in the step (2), concentrating the filtrate until the manganese content is 150-220 g/L, and adding H₂SO₄Adjusting the pH value to 5.5-6.5, connecting the pH value with a direct concentration tank heated by a coil pipe in series to Be concentrated to 58Be, continuously feeding and directly concentrating, continuously producing crystals, pre-concentrating mother liquor, spin-drying the crystals in a centrifugal machine, and drying to obtain high-purity manganese sulfate MnSO with the manganese content of more than or equal to 99.5 percent₄·H₂And (4) O products.

2. The method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction to treat manganese oxide ore according to claim 1, wherein the enzyme is 1-2 of inulinase, maltase, glucolase or fructosidase, and the auxiliary reducing agent is Fe, FeO or FeSO₃1-2 kinds of them.

3. The method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction manganese oxide ore according to claim 1, wherein the step (1) comprises the steps of mixing 900kg of manganese oxide ore containing 22% of manganese and 250kg of manganese carbosulfate ore containing 20% of manganese at 10m³1.5m is injected into the reaction tank³Clear water, react to the end and then add 4.6m³The clear water contains 147 kg of concentrated sulfuric acid, 0.18-0.22 kg of enzyme and 72-74 kg of auxiliary reducing agent.

4. The method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction treatment manganese oxide ore according to claim 1, wherein the step (1) for removing iron and reducing acid is to add hydrogen peroxide and dilute ammonia water under the condition of stirring or blowing.

5. The method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction manganese oxide ore according to claim 1, wherein BaS can be added in the step (1) to remove heavy metal ions.

6. The method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction to treat manganese oxide ore according to claim 1, wherein manganese sulfate containing more than or equal to 99.5% of manganese is refined into high-purity manganese sulfate MnSO containing more than or equal to 99.9% mn₄.H₂O is prepared by the step (3) of obtaining high-purity manganese sulfate MnSO with the manganese content of more than or equal to 99.5 percent₄·H₂Placing O in exchange water of 15-20 kilomega ohm cm, preparing a solution according to the concentration of 80-100 g/LMn for dissolving for 2 minutes, filtering, concentrating the filtrate in a rising film concentrator, keeping the vacuum degree of 510-620 mmHg, and keeping the steam pressure of 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 75-85 ℃ until manganese is contained in 130-140 g/L, adding HF into a reaction vessel with stirring according to the proportion of 1.0-1.4 times of the sum of CaO and MgO for reacting for 30-40 minutes, and then adding 6-9 kg/m³Adding food-grade wood activated carbon powder into the mixture according to the proportion, reacting for 30-40 minutes, standing for 1-2 hours according to the proportion of 0.03kg/m³Adding chemical pure (NH4)₂S, reacting for 20-30 minutes, standing for 24 hours, extracting slag liquid, finely filtering, concentrating filtrate until the filtrate contains 180-220 g/L of manganese, adding sulfuric acid to adjust the pH value to Be 5.5-6.5, connecting the filtrate with a direct concentration tank heated by a coil pipe in series until the concentration is more than or equal to 58Be degrees, continuously adding materials and directly concentrating, continuously producing crystals, adding mother liquor into pre-concentrated crystals, spin-drying the mother liquor in a centrifugal machine, and drying to obtain high-purity MnSO manganese sulfate with the concentration of more than or equal to 99.9% mn₄.H₂And (4) O products.

Technical Field

The invention relates to the technical field of hydrometallurgy, in particular to a method for producing high-purity manganese sulfate by reducing manganese oxide ore through hydroxyl combined liquid phase.

Background

The high-purity manganese sulfate is a high-tech product and a high-grade product, and can be further developed: (ii) electronic grade products, e.g. Mn₃O₄、MnCO₃The like are used as basic raw material components of the electronic grade soft magnetic ferrite; ② the electrical porcelain material of lithium manganate; high-grade chemical raw materials such as manganese acetate and the like used as the catalyst; fourthly, the product is used as medical health care products such as manganese phosphate, manganese hypophosphite, manganese gluconate, manganese citrate and the like. Fifthly, taking high-purity sulfuric acid as a raw material, a plurality of new manganese chemical products can be developed and widely applied in the modern high-tech field, such as TiMn1.5, ZrMn2, ZrMnFe1.2 and the like which can be used as memory alloy and hydrogen storage alloy, new semiconductor and electronic material, excited light semiconductor material, etc,Piezoelectric materials, ferromagnetic materials, and the like.

The high-purity manganese sulfate is used for developing electrolytic manganese metal, industrial manganese sulfate, feed-grade manganese sulfate and the like, and is favored and praised by manufacturers and users due to low cost and good product quality; the development of new technical products by using the method and the device can prolong the industrial chain, is the requirement of enterprise development, and is also completely possible, so the cost is lower, and the benefit is better.

Disclosure of Invention

The invention aims to provide a method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore, which can produce high-purity MnSO with the purity of more than or equal to 99 percent₄.H₂O。

The invention achieves the above purposes through the following technical scheme: a method for producing high-purity manganese sulfate by using hydroxyl combined liquid phase reduction treatment manganese oxide ore comprises the following steps:

(1) removing iron, acid and heavy metal ions from the crude manganese sulfate solution: injecting clean water into a reaction tank, adding manganese oxide ore containing 22% of manganese and manganese carbosulfate ore containing 20% of manganese, adding enzyme and a reducing aid, preheating the clean water to 70-72 ℃, reacting for 3.5-4.5 h at the reaction temperature of 90-93 ℃ after the addition of the materials, filtering, washing the slag once with the clean water to obtain filtrate and washing liquid, wherein the step of removing iron and reducing acid is to slowly flow industrial hydrogen peroxide and industrial ammonia water with the concentration of 1:1 into the washing liquid to ensure that the pH value of the liquid is 5.4 and keep the liquid unchanged for 25 minutes, and then, adding the following components: 0.6-0.9 kg/m sodium ferulate³Adding sodium ferbamate according to the proportion, stirring for 40 minutes after adding, sampling and analyzing whether Co and Ni are qualified or not, performing filter pressing to obtain qualified liquid and slag, taking the filtrate as deep purification liquid, taking the slag as a raw material for recovering Co and Ni,

(2) deep purification of filtrate: concentrating the filtrate obtained in the step (1), and keeping the vacuum degree of 510-620 mmHg in a rising film concentrator and the vapor pressure of 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 70-72 ℃ until the manganese content is 120-140 g/L, and adding F according to the proportion of 1.0-1.4 times of the sum of CaO and MgO^-Reacting for 30-40 minutes, and then reacting according to the proportion of 3-8 kg/m³Adding active carbon to react for 30-40 minStanding for 1-2 h at a rate of 0.03kg/m³Is added in a proportion of (NH)₄)₂S, reacting for 20-30 minutes, and standing for 24 hours;

(3) fine filtering the supernatant obtained in the step (2), concentrating the filtrate until the manganese content is 150-220 g/L, and adding H₂SO₄Adjusting the pH value to 5.5-6.5, connecting the pH value with a direct concentration tank heated by a coil pipe in series to Be concentrated to 58Be, continuously feeding and directly concentrating, continuously producing crystals, pre-concentrating mother liquor, spin-drying the crystals in a centrifugal machine, and drying to obtain high-purity manganese sulfate MnSO with the manganese content of more than or equal to 99.5 percent₄·H₂And (4) O products.

The enzyme is 1-2 of inulinase, maltase, glucolase or fructosidase, and the auxiliary reducing agent is Fe, FeO or FeSO₃1-2 kinds of them.

The step (1) is that 900kg of manganese oxide ore containing 22 percent of manganese and 250kg of carbon manganese sulfate ore containing 20 percent of manganese are added in 10m³1.5m is injected into the reaction tank³Clear water, react to the end and then add 4.6m³The clear water contains 147 kg of concentrated sulfuric acid, 0.18-0.22 kg of enzyme and 72-74 kg of auxiliary reducing agent.

In the step (1), iron removal and acid reduction are carried out by adding hydrogen peroxide and dilute ammonia water under the condition of stirring or blowing.

BaS can be added in the step (1) to remove heavy metal ions.

Refining manganese sulfate with manganese content of more than or equal to 99.5 percent into high-purity manganese sulfate MnSO with manganese content of more than or equal to 99.9 percent mn₄.H₂O is prepared by the step (3) of obtaining high-purity manganese sulfate MnSO with the manganese content of more than or equal to 99.5 percent₄·H₂Placing O in exchange water of 15-20 kilomega ohm cm, preparing a solution according to the concentration of 80-100 g/LMn for dissolving for 2 minutes, filtering, concentrating the filtrate in a rising film concentrator, keeping the vacuum degree of 510-620 mmHg, and keeping the steam pressure of 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 75-85 ℃ until manganese is contained in 130-140 g/L, adding HF into a reaction vessel with stirring according to the proportion of 1.0-1.4 times of the sum of CaO and MgO for reacting for 30-40 minutes, and then adding 6-9 kg/m³Adding food-grade wood activated carbon powder into the mixture according to the proportion, reacting for 30-40 minutes, standing for 1-2 hours according to the proportion of 0.03kg/m³Adding chemical pure (NH4)₂S, reacting for 20-30 minutes, standing for 24 hours, extracting slag liquid, finely filtering, concentrating filtrate until the filtrate contains 180-220 g/L of manganese, adding sulfuric acid to adjust the pH value to Be 5.5-6.5, connecting the filtrate with a direct concentration tank heated by a coil pipe in series until the concentration is more than or equal to 58Be degrees, continuously adding materials and directly concentrating, continuously producing crystals, adding mother liquor into pre-concentrated crystals, spin-drying the mother liquor in a centrifugal machine, and drying to obtain high-purity MnSO manganese sulfate with the concentration of more than or equal to 99.9% mn₄.H₂And (4) O products.

The invention has the outstanding advantages that:

1. the process adopts a method combining chemical method for removing Ca and Mg and physical method for removing Ca and Mg, the effect is very obvious, Ca can be removed to 0.0014g/L (18 ℃), and Mg can be removed to 0.0076g/L18 ℃.

2. The equipment adopts a decompression concentration device, namely a direct concentration mode of heating by a climbing film concentrator and a coil pipe is combined, the crystallization process is continuously carried out, the innovation in the industry is realized, and the energy can be saved by 30-50% in the whole process.

3. Adopts food-grade active carbon for deep purification, effectively removes iron and heavy metal ions, and can remove more than 50 percent of residual Cl^-。

Detailed Description

The technical solution of the present invention is further illustrated by the following examples.

Example 1

This example is an example of the method for producing high-purity manganese sulfate by using hydroxyl group combined liquid phase reduction to treat manganese oxide ore according to the present invention, and includes the following steps:

1. at 10m³1.5m is injected into the reaction tank³Clear water, react to the end and then add 4.6m³900kg of manganese oxide ore containing 22% of manganese and 250kg of carbon manganese sulfate ore containing 20% of manganese are added into the clean water, and 147 kg of concentrated sulfuric acid is added. 0.18-0.22 kg of enzyme, wherein the enzyme is 1-2 of inulinase, maltose, glucose or fructose, the auxiliary reducing agent is 72-74 kg, and the auxiliary reducing agent is Fe, FeO or FeSO₃When the clear water is preheated to 70-72 ℃, the reaction temperature after the addition of the materials can reach 90-93 ℃, and the reaction lasts for 3.5-4.5 hFiltering, washing the residue with 150L of clear water once, the residue containing 1.4% manganese, and the filtrate and wash solution 8.8m³，H⁺22.86g/L, no Fe. Containing manganese 37.82kg/m³The leaching rate of manganese is 97.13 percent calculated by liquid. The pH of the filtrate is 3-3.5. Removing iron and reducing acid: at 8.8m³The industrial hydrogen peroxide and the industrial ammonia water with the concentration of 1:1 are slowly flowed into the filter washing liquid, the pH value of the liquid is 5.4, and the liquid is kept for 25 minutes, and the Fe in the liquid is less than or equal to 1.5-2.0 mg/L. Followed by a pressure of 0.6 to 0.9kg/m³Adding sodium ferbamate according to the proportion, stirring for 40 minutes after adding, sampling and analyzing whether Co and Ni are qualified, or else, adding or prolonging the reaction time until the Co and Ni are qualified. Filter-pressing the qualified liquid, and taking the slag as a raw material for recovering Co and Ni to be sold; the solution contains Mn 34-38 g/L and has a pH of 6.5-6.8.

2. Concentrating the filtrate obtained in the step 1, and keeping the vacuum degree of 510-620 mmHg in a rising film concentrator and the vapor pressure of 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 70-72 ℃ until the manganese content is 120-140 g/L, and adding F according to the proportion of 1.0-1.4 times of the sum of CaO and MgO^-Reacting for 30-40 minutes, and then reacting according to the proportion of 3-8 kg/m³Adding active carbon to react for 30-40 minutes, standing for 1-2 hours according to the proportion of 0.03kg/m³Is added in a proportion of (NH)₄)₂And S is reacted for 20-30 minutes and kept stand for 24 hours.

3. Fine filtering the supernatant obtained in the step 2, and concentrating the filtrate until the manganese content is 150-220 g/L or 52B DEG_eAnd adding H₂SO₄Adjusting the pH value to 5.5-6.5, connecting the concentration tank with a direct concentration tank heated by a coil pipe in series to obtain a concentrated solution with the concentration of 58Be degrees, continuously feeding the concentrated solution to directly concentrate the concentrated solution, and continuously producing crystals. Mother liquor is pre-concentrated, crystals are dried by a centrifuge, and then high-purity manganese sulfate MnSO with manganese content more than or equal to 99.5 percent is obtained by drying₄·H₂And (4) O products.

Example 2

This example is an example of preparing ultra-high purity manganese sulfate having manganese sulfate greater than or equal to 99.9% Mn.

Putting the product manganese sulfate containing more than or equal to 99.5 percent of Mn in example 1 into exchange water of 15-20 kilomega-cm, dissolving the product manganese sulfate in a solution according to the concentration of 80-100 g/LMn for 2 minutes, and returning the insoluble substances to the step 2 in example 1 without pre-neutralizationAnd in the concentrated solution; concentrating the soluble substance in a steel film-rising concentrator, keeping the vacuum degree at 510-620 mmHg and the vapor pressure at 0.4-1.0 kg/cm²Evaporation intensity > 100kg/m²Concentrating at 75-85 ℃ until manganese is contained 130-140 g/L, adding HF into a reaction vessel with a stirrer according to the proportion of 1.0-1.4 times of the sum of CaO and MgO for reacting for 30-40 minutes, wherein the liquid temperature is not less than 70 ℃, and then reacting according to the proportion of 6-9 kg/m³Adding food-grade wood activated carbon powder into the mixture according to the proportion, reacting for 30-40 minutes, standing for 1-2 hours according to the proportion of 0.03kg/m³Adding chemical pure (NH4)₂And S, reacting for 20-30 minutes, and standing for 24 hours. And (3) extracting residue liquid, carrying out fine filtration, concentrating the filtrate until the manganese content is 180-220 g/L or more than or equal to 52Be degrees, adding sulfuric acid to adjust the pH value to Be 5.5-6.5, connecting the filtrate in series with a direct concentration tank heated by a coil pipe until the pH value is more than or equal to 58Be degrees, continuously feeding the material, directly concentrating, and continuously producing crystals. The mother liquor is added into the preconcentrated crystal, and dried after being spin-dried by a centrifuge, so that high-purity manganese sulfate MnSO with the mn of more than or equal to 99.9 percent is obtained₄.H₂And (4) O products.