阅读说明：本技术 一种利用氯化铜锰液制备工业级碳酸锰的方法 (Method for preparing industrial manganese carbonate by using copper-manganese chloride solution ) 是由 曹栋强 龚丽锋 王红忠 黄飞中 方志国 罗瑞平 于 2020-05-12 设计创作，主要内容包括：本发明公开了一种利用氯化铜锰液制备工业级碳酸锰的方法,其特征在于：包括如下步骤：所述S1置换铜：向铜锰液中加入铁粉,反应完全后,滤去铜渣,得到除铜后液,除铜后,溶液中仅含铜0.04g/L,铜的回收率达99.2%；S2除钙铁铝：向除铜后液中加入P507萃余液。反应完全后,再加入双氧水。氧化完全后,再缓慢加入碱性物质,进一步反应完全后,滤去废渣,分离得除钙铁铝后液；S3沉锰：向除钙铁铝后液中,缓慢加入可溶性碳酸盐,进行碳酸化沉淀锰,将锰以及其他少量金属离子沉淀下来,过滤得到粗碳酸锰。本发明处理流程较短,工艺简单,置换铜、除杂、沉锰,分为三步骤完成,只采用了三次过滤分离。铜锰以外的大部分杂质金属元素在除杂步骤以共沉淀的形式除去。(The invention discloses a method for preparing industrial manganese carbonate by using copper-manganese chloride solution, which is characterized by comprising the following steps: the method comprises the following steps: the S1 displacement copper: adding iron powder into the copper-manganese solution, filtering copper slag after the reaction is completed to obtain a copper-removed solution, wherein the solution only contains 0.04g/L of copper after the copper is removed, and the recovery rate of the copper reaches 99.2%; s2 removing calcium, iron and aluminum: adding P507 raffinate into the copper-removed liquid. After the reaction is completed, hydrogen peroxide is added. After complete oxidation, slowly adding an alkaline substance, further completely reacting, filtering out waste residues, and separating to obtain a liquid after calcium, iron and aluminum removal; s3 precipitation of manganese: slowly adding soluble carbonate into the solution after calcium, iron and aluminum removal, carrying out carbonation to precipitate manganese, precipitating manganese and other small amount of metal ions, and filtering to obtain crude manganese carbonate. The method has the advantages of short treatment flow, simple process, copper replacement, impurity removal and manganese precipitation, and is completed by three steps, and only three times of filtration and separation are adopted. Most impurity metal elements except copper and manganese are removed in a coprecipitation mode in the impurity removing step.)

1. A method for preparing industrial manganese carbonate by using copper manganese chloride solution is characterized by comprising the following steps: the method comprises the following steps:

s1 substitution of copper: adding iron powder into the copper-manganese solution, filtering copper slag after the reaction is completed to obtain a copper-removed solution, wherein the solution only contains 0.04g/L of copper after the copper is removed, and the recovery rate of the copper reaches 99.2%;

s11: 500ml of copper-manganese solution is put into a 2L beaker, and the components of the copper-manganese solution are 4.8g/L of copper, 82.3g/L of manganese, 19.6g/L of calcium and 7.1g/L of aluminum for standby;

s12: heating the copper-manganese solution for later use in a water bath at 60 ℃, adding 3.0g of iron powder, stirring for reaction for 1 hour, and filtering to remove copper slag to obtain a copper-removed solution;

s2 removing calcium, iron and aluminum: adding P507 raffinate into the copper-removed liquid;

after the reaction is completed, adding hydrogen peroxide;

after complete oxidation, slowly adding an alkaline substance, further completely reacting, filtering out waste residues, and separating to obtain a liquid after calcium, iron and aluminum removal;

s21: adding 500ml of P507 raffinate into the copper-removed solution, and stirring and reacting for 1 hour for later use;

s22: then 8ml of hydrogen peroxide is slowly added into the solution, and the mixture is reacted for half an hour for standby;

s23: then Na with the concentration of 10 percent is slowly added₂CO₃Adjusting the pH value of the solution to 4.1, and continuously reacting for one hour;

after the reaction is finished, carrying out suction filtration to obtain filtrate which is the solution after iron, aluminum and calcium are removed;

s3 precipitation of manganese: slowly adding soluble carbonate into the calcium-iron-aluminum-removed solution, carrying out carbonation to precipitate manganese, precipitating manganese and other small metal ions, and filtering to obtain crude manganese carbonate;

s31: removing calcium, iron and aluminum, adding Na gradually at room temperature₂CO₃Adjusting the pH value of the solution to 7.5 by using solid powder, and stirring and reacting for one hour for later use;

s32: and filtering the standby solution, washing and drying the manganese slag to obtain crude manganese carbonate, wherein the manganese content is 42%, and the recovery rate of manganese reaches 96%.

2. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: and the using amount of the iron powder in the S1 is 1.1-1.5 times of the theoretical molar amount of the copper.

3. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the copper replacement process in the S1 is realized at the temperature of 50-70 ℃, and the reaction time is 1.0-3.0 h.

4. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the addition amount of the P507 raffinate in the S2 is 1-2 times of that of the copper-manganese liquid, and the usage amount of the hydrogen peroxide is 1.1-1.5 times of the theoretical molar amount required by the ferrous oxide ions.

5. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: and the alkaline substance in the S2 is one or a mixture of more of sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia water and ammonium carbonate, and the pH value of the solution is adjusted to 4-5.

6. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the coupling agent is one or a mixture of more of propyl orthosilicate and ethyl orthosilicate.

7. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: and (3) finishing the reaction process in the S2 under the heating condition of 50-70 ℃, wherein the reaction time is 2-4 h, and filtering while the reaction is hot after the reaction is finished.

8. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the carbonating manganese precipitation process in the S3 can be completed at normal temperature, and the manganese precipitation time is 1-2 h.

9. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the soluble carbonate in the S3 is one or a mixture of more of sodium carbonate, sodium bicarbonate, ammonium bicarbonate and the like, and the final pH value of the precipitated manganese is 7-8.

10. The method for preparing industrial-grade manganese carbonate by using the copper-manganese chloride liquid as claimed in claim 1, wherein the method comprises the following steps: the copper chloride manganese solution in the S1 is generated in the process of preparing cobalt salt, wherein the main valuable metals are manganese (30-100g/L), copper (5-30g/L), the contents of cobalt and zinc are low (< 1g/L), in addition, calcium (5-30g/L), aluminum (2-10g/L) and free acid (0.1-2.0 mol/L) are also generated, and the P507 raffinate in the invention is also generated in the process of preparing cobalt salt, and mainly contains nickel (50-300mg/L), magnesium (0.2-1g/L), sodium (10-30g/L) and a large amount of free sulfate ions (50-100 g/L).

Technical Field

The invention relates to the technical field of heavy metal industrial wastewater treatment, in particular to a method for preparing industrial manganese carbonate by using a copper manganese chloride solution.

Background

In the process of preparing cobalt salt from cobalt ore and cobalt intermediate products, a backwash liquid obtained after P204 extraction and impurity removal is an acid chloride solution containing a large amount of metal ions such as copper, manganese and the like, and is called copper-manganese liquid. In the traditional method for treating the wastewater containing the heavy metal ions, the heavy metal ions are mainly precipitated and separated from the wastewater, for example, the methods adopted by most enterprises for treating the copper-manganese waste liquid include a lime neutralization method, an alkali neutralization method and the like. However, the treatment generates a large amount of copper-manganese slag, the treatment cost of hazardous wastes is high, and secondary pollution can be generated. At present, a lot of related researches on resource utilization of copper-manganese waste liquid exist. For example, in patent CN105296754, crude manganese carbonate is obtained by removing calcium, depositing copper, replacing cobalt, and the like step by step, and finally depositing manganese. The method disclosed in patent CN105967217 is improved to a certain extent, and insoluble carbonate is used for copper precipitation, so that solid-liquid separation is facilitated. But Cu²⁺pH value and Mn of precipitate²⁺The manganese recovery rate is influenced inevitably in the copper deposition process. Patent CN108585051 and patent CN 102242266 disclose the use of a copper-manganese chloride solution to prepare battery-grade manganese sulfate, wherein the former is a recrystallization method, and the latter is an extraction separation method, but both have the problems of complex process and high production cost, and sulfide and fluoride are required to be added for deeply removing impurity metals, which easily causes environmental pollution. In the process of preparing cobalt salt from cobalt ore and cobalt intermediate products, raffinate obtained after extracting cobalt by P507 is also a waste liquid generated in the production of cobalt salt, and contains a small amount of nickel, magnesium and high-concentration sodium sulfate. The traditional treatment method of the P507 raffinate is to recover nickel in the raffinate by a chemical precipitation method or an ion exchange method, and sodium sulfate in the raffinate is not treated, so that certain resource waste is caused.

Disclosure of Invention

The invention aims to provide a method for preparing industrial manganese carbonate by using a copper manganese chloride solution, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: s1 substitution of copper: and adding iron powder into the copper-manganese solution, filtering copper slag after the reaction is completed to obtain a copper-removed solution, wherein the solution only contains 0.04g/L of copper after the copper is removed, and the recovery rate of the copper reaches 99.2%.

S11, putting 500ml of copper-manganese solution into a 2L beaker, wherein the copper-manganese solution comprises 4.8g/L copper, 82.3g/L manganese, 19.6g/L calcium and 7.1g/L aluminum for later use;

s12: heating the copper-manganese solution for later use in a water bath at 60 ℃, adding 3.0g of iron powder, stirring for reaction for 1 hour, and filtering to remove copper slag to obtain a copper-removed solution;

s2 removing calcium, iron and aluminum: adding P507 raffinate into the copper-removed liquid. After the reaction is completed, hydrogen peroxide is added. After complete oxidation, slowly adding an alkaline substance, further completely reacting, filtering out waste residues, and separating to obtain a liquid after calcium, iron and aluminum removal;

s21, adding 500ml of P507 raffinate into the copper-removed solution, and stirring and reacting for 1 hour for later use;

s22, slowly adding 8ml of hydrogen peroxide into the solution, and reacting for half an hour for later use;

s23, slowly adding Na with the concentration of 10 percent₂CO₃The solution was adjusted to pH 4.1 and the reaction was continued for one hour. After the reaction is finished, carrying out suction filtration to obtain filtrate which is the solution after iron, aluminum and calcium are removed.

S3 precipitation of manganese: slowly adding soluble carbonate into the solution after calcium, iron and aluminum removal, carrying out carbonation to precipitate manganese, precipitating manganese and other small amount of metal ions, and filtering to obtain crude manganese carbonate.

S31: removing calcium, iron and aluminum, adding Na gradually at room temperature₂CO₃Adjusting the pH value of the solution to 7.5 by using solid powder, and stirring and reacting for one hour for later use;

s32: and filtering the standby solution, washing and drying the manganese slag to obtain crude manganese carbonate, wherein the manganese content is 42%. The recovery rate of manganese reaches 96 percent.

Preferably, the using amount of the iron powder in the S1 is 1.1-1.5 times of the theoretical molar amount of the copper.

Preferably, the copper replacement process in S1 is realized at the temperature of 50-70 ℃, and the reaction time is 1.0-3.0 h.

Preferably, the addition amount of the P507 raffinate in the S2 is 1-2 times of that of the copper-manganese liquid, and the usage amount of the hydrogen peroxide is 1.1-1.5 times of the theoretical molar amount of the ferrous oxide ions.

Preferably, the alkaline substance in the S2 is one or a mixture of more of sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia water and ammonium carbonate, and the pH value of the solution is adjusted to 4-5.

Preferably, the reaction process in the S2 is completed under the heating condition of 50-70 ℃, the reaction time is 2-4 h, and the hot solution is filtered after the reaction is finished.

Preferably, the carbonating manganese precipitation process in the step S3 can be completed at normal temperature, and the manganese precipitation time is 1-2 hours.

Preferably, the soluble carbonate in S3 is one or a mixture of sodium carbonate, sodium bicarbonate, ammonium bicarbonate and the like, and the final pH value of the precipitated manganese is 7-8.

Preferably, the copper chloride manganese solution is generated in the process of preparing cobalt salt, wherein the main valuable metals are manganese (30-100g/L) and copper (5-30g/L), the contents of cobalt and zinc are low (< 1g/L), and in addition, calcium (5-30g/L), aluminum (2-10g/L) and free acid (0.1-2.0 mol/L) are also contained. The P507 raffinate in the invention is also generated in the process of preparing cobalt salt, and mainly contains nickel (50-300mg/L), magnesium (0.2-1g/L), sodium (10-30g/L) and a large amount of free sulfate ions (50-100 g/L).

Compared with the prior art, the invention has the beneficial effects that:

1. the invention has the advantages of short whole treatment flow, simple process, copper replacement, impurity removal and manganese precipitation, and is completed by three steps, and only three times of filtration and separation are adopted. Most impurity metal elements except copper and manganese are removed in a coprecipitation mode in the impurity removal step;

2. the invention has low production cost, adopts P507 raffinate to replace soluble sulfate precipitator for calcium removal, comprehensively utilizes the sulfate in the P507 raffinate, and greatly reduces the treatment cost of calcium removal;

3. the treatment process of the invention does not need to use sulfide and fluoride, and the final wastewater has no harmful substance, neutral pH, environmental protection and no pollution.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a technical scheme that: