阅读说明：本技术 一种从电解锰阳极渣中回收锰、铅的方法 (Method for recovering manganese and lead from electrolytic manganese anode slag ) 是由 董雄文 董雄武 倪敏 郭华军 于 2020-12-23 设计创作，主要内容包括：本发明公开了一种从电解锰阳极渣中回收锰、铅的方法,包括：(1)对阳极渣进行磨细处理；(2)将粉料加入还原炉中,通入氨分解制得的氢气,进行还原反应,锰渣中的铅经高温蒸发成气体；(3)将气体经水冷却,气体中的铅蒸汽冷却成固态的铅；(4)将还原后的锰渣加入稀硫酸溶液中进行反应,生成硫酸锰混合浆料；(5)将硫酸锰混合浆料进行压滤,滤液为硫酸锰溶液；(6)向硫酸锰溶液中加入氧化剂,进行氧化除铁,过滤后得到纯净的硫酸锰溶液。本发明提供一种从电解锰阳极渣中回收锰、铅的方法,该方法可以有效地回收阳极渣中的锰、铅元素,对阳极渣进行有效治理并资源化利用,既解决了阳极渣污染环境的问题,又实现了有价资源的回收。(The invention discloses a method for recovering manganese and lead from electrolytic manganese anode slag, which comprises the following steps: (1) grinding the anode slag; (2) adding the powder into a reduction furnace, introducing hydrogen prepared by ammonia decomposition, carrying out reduction reaction, and evaporating lead in the manganese slag into gas at high temperature; (3) cooling the gas by water, and cooling lead steam in the gas into solid lead; (4) adding the reduced manganese slag into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry; (5) carrying out filter pressing on the manganese sulfate mixed slurry, wherein the filtrate is a manganese sulfate solution; (6) adding an oxidant into the manganese sulfate solution, performing oxidation deferrization, and filtering to obtain a pure manganese sulfate solution. The invention provides a method for recovering manganese and lead from electrolytic manganese anode slag, which can effectively recover manganese and lead elements in the anode slag, effectively treat and recycle the anode slag, solve the problem of environmental pollution of the anode slag and realize the recovery of valuable resources.)

1. A method for recovering manganese and lead from electrolytic manganese anode slag is characterized by comprising the following steps:

(1) grinding the anode slag to obtain powder with preset fineness;

(2) adding the powder obtained in the step (1) into a reduction furnace, introducing hydrogen gas prepared by ammonia decomposition, carrying out reduction reaction, reducing manganese dioxide in manganese slag into manganese monoxide, and evaporating lead in the manganese slag into gas at high temperature to obtain reduced manganese slag;

(3) cooling the gas obtained in the step (2) by water, and cooling lead steam in the gas into solid lead to obtain a lead concentrate product;

(4) adding the reduced manganese slag obtained in the step (2) into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry;

(5) performing filter pressing on the manganese sulfate mixed slurry obtained in the step (4), wherein the obtained filter residue is leaching residue, and the filtrate is manganese sulfate solution;

(6) and (5) adding an oxidant into the manganese sulfate solution obtained in the step (5), carrying out oxidation iron removal, and filtering to obtain a pure manganese sulfate solution which can be directly used as an electrolytic manganese raw material.

2. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 1, wherein in the step (1), the fineness of the powder with the predetermined fineness is-0.075 mm and accounts for more than 80%.

3. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 1, wherein in the step (2), the temperature of the reduction reaction is 700-1200 ℃.

4. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 3, wherein the temperature of the reduction reaction is 800-1000 ℃.

5. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 1, wherein in the step (5), the leached slag is subjected to harmless treatment and then is transported to a slag yard for storage.

6. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 1, wherein in the step (6), the oxidant is one or more of oxygen, hydrogen peroxide and manganese dioxide.

7. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 1, wherein in the step (6), the iron-removed slag obtained by filtering is calcined at low temperature to obtain cement blending material which can be sold to cement factories.

8. The method for recovering manganese and lead from electrolytic manganese anode slag according to claim 7, wherein the low-temperature calcination temperature is 300-520 ℃.

Technical Field

The invention belongs to the technical field of manganese slag recovery, and relates to a method for recovering manganese and lead from electrolytic manganese anode slag.

Background

China is the biggest world manganese production, consumption and export, and accounts for more than 90% of the total global manganese production. The manganese slag in the wet manganese industry is a general name for leached manganese slag, manganese sulfide slag and anode slag in the production of electrolytic manganese metal, electrolytic manganese dioxide and manganese sulfate products. The manganese slag yield in China in 2019 is reported to exceed 2000 ten thousand tons.

When the metal manganese is electrolyzed to produce, in a diaphragm electrolytic cell, a manganese sulfate aqueous solution containing ammonium sulfate is taken as electrolyte, direct current is introduced, the metal manganese is deposited on a cathode, hydrogen is separated out, and other metal ions are also separated out in a trace amount at the cathode and mixed in a manganese sheet; oxygen is separated out on the anode, and a small amount of manganese dioxide sediment is formed, namely the anode slag. In industrial production, lead, antimony, tin, silver and other multi-element alloys are generally selected as anode materials, and stainless steel plates are selected as cathode materials. The anode slag generally contains about 40% of manganese which mainly exists in the form of manganese dioxide and 1.5% -6% of valuable metals such as lead and the like.

At present, most of domestic enterprises transport anode slag to a storage yard for damming and stacking, and not only seriously damage the ecological environment but also waste heavy metal elements in the anode slag under the effect of weathering leaching for a long time.

Disclosure of Invention

The invention aims to provide a method for recovering manganese and lead from electrolytic manganese anode slag, which can effectively recover manganese and lead elements in the electrolytic manganese anode slag.

The method for recovering manganese and lead from electrolytic manganese anode slag provided by the invention comprises the following steps:

(1) grinding the anode slag to obtain powder with preset fineness;

(2) adding the powder obtained in the step (1) into a reduction furnace, introducing hydrogen gas prepared by ammonia decomposition, carrying out reduction reaction, reducing manganese dioxide in manganese slag into manganese monoxide, and evaporating lead in the manganese slag into gas at high temperature to obtain reduced manganese slag;

(3) cooling the gas obtained in the step (2) by water, and cooling lead steam in the gas into solid lead to obtain a lead concentrate product;

(4) adding the reduced manganese slag obtained in the step (2) into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry;

(5) performing filter pressing on the manganese sulfate mixed slurry obtained in the step (4), wherein the obtained filter residue is leaching residue, and the filtrate is manganese sulfate solution;

(6) and (5) adding an oxidant into the manganese sulfate solution obtained in the step (5), carrying out oxidation iron removal, and filtering to obtain a pure manganese sulfate solution which can be directly used as an electrolytic manganese raw material.

Preferably, in the step (1), the fineness of the powder with the preset fineness is-0.075 mm and accounts for more than 80%.

Preferably, in the step (2), the temperature of the reduction reaction is 700-1200 ℃.

Further, in the step (2), the temperature of the reduction reaction is 800 ℃ to 1000 ℃.

Preferably, in the step (5), the leached slag is subjected to harmless treatment and then is transported to a slag yard for stockpiling.

Preferably, in the step (6), the oxidant is one or a combination of more of oxygen, hydrogen peroxide and manganese dioxide.

In the preferable scheme, in the step (6), the iron-removed slag obtained by filtering is calcined at low temperature to obtain the cement blending material which can be sold to a cement plant.

Further, the low-temperature calcination temperature is 300-520 ℃.

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

the invention provides a method for recovering manganese and lead from electrolytic manganese anode slag, which can effectively recover manganese and lead elements in the anode slag, effectively treat and recycle the anode slag, solve the problem of environmental pollution of the anode slag and realize the recovery of valuable resources.

Drawings

FIG. 1 is a process flow diagram of example 1 of the present invention.

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, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.

In this example, unless otherwise specified, all reagents used were common commercial products or prepared by conventional means, and the equipment used was conventional in the art, and the following are some examples of the inventors in the experiment:

in the embodiment of the invention, the anode slag comprises the following main components in percentage by mass: mn (30-50%), Pb (1.5-6%), S (3-8%) and Fe (0.1-1%).

Example 1

The invention relates to a method for recovering manganese and lead from electrolytic manganese anode slag, which comprises the following steps:

(1) feeding the anode slag into a flour mill for dry milling, returning coarse materials to the flour mill for regrinding through a particle classifier to obtain powder with the fineness of-0.075 mm accounting for more than 80%, and feeding qualified fine materials into the next process;

(2) adding the powder obtained in the step (1) into a reduction furnace, controlling the temperature to be 800 ℃, introducing hydrogen gas prepared by ammonia decomposition, carrying out reduction reaction, reducing manganese dioxide in manganese slag into manganese monoxide, and evaporating lead in the manganese slag into gas at high temperature to obtain reduced manganese slag;

(3) cooling the gas obtained in the step (2) by water, and cooling lead steam in the gas into solid lead to obtain a lead concentrate product;

(4) adding the reduced manganese slag obtained in the step (2) into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry;

(5) performing filter pressing on the manganese sulfate mixed slurry obtained in the step (4), wherein the obtained filter residue is leaching residue, and the filtrate is manganese sulfate solution;

(6) and (5) adding hydrogen peroxide into the manganese sulfate solution obtained in the step (5), performing oxidation iron removal, and filtering to obtain a pure manganese sulfate solution which can be directly used as an electrolytic manganese raw material.

Example 2

The invention relates to a method for recovering manganese and lead from electrolytic manganese anode slag, which comprises the following steps:

(1) feeding the anode slag into a flour mill for dry milling, returning coarse materials to the flour mill for regrinding through a particle classifier to obtain powder with the fineness of-0.075 mm accounting for more than 80%, and feeding qualified fine materials into the next process;

(2) adding the powder obtained in the step (1) into a reduction furnace, controlling the temperature to be 1200 ℃, introducing hydrogen gas prepared by ammonia decomposition, carrying out reduction reaction, reducing manganese dioxide in manganese slag into manganese monoxide, and evaporating lead in the manganese slag into gas at high temperature to obtain reduced manganese slag;

(3) cooling the gas obtained in the step (2) by water, and cooling lead steam in the gas into solid lead to obtain a lead concentrate product;

(4) adding the reduced manganese slag obtained in the step (2) into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry;

(5) performing filter pressing on the manganese sulfate mixed slurry obtained in the step (4), wherein the obtained filter residue is leaching residue, and the filtrate is manganese sulfate solution;

(6) adding manganese dioxide into the manganese sulfate solution obtained in the step (5), carrying out oxidation iron removal, filtering to obtain a pure manganese sulfate solution which can be directly used as an electrolytic manganese raw material, filtering to obtain iron-removed slag, and calcining at 300 ℃ to obtain a cement blending material.

Example 3

The invention relates to a method for recovering manganese and lead from electrolytic manganese anode slag, which comprises the following steps:

(1) feeding the anode slag into a flour mill for dry milling, returning coarse materials to the flour mill for regrinding through a particle classifier to obtain powder with the fineness of-0.075 mm accounting for more than 80%, and feeding qualified fine materials into the next process;

(2) adding the powder obtained in the step (1) into a reduction furnace, controlling the temperature to be 700 ℃, introducing hydrogen gas prepared by ammonia decomposition, carrying out reduction reaction, reducing manganese dioxide in manganese slag into manganese monoxide, and evaporating lead in the manganese slag into gas at high temperature to obtain reduced manganese slag;

(3) cooling the gas obtained in the step (2) by water, and cooling lead steam in the gas into solid lead to obtain a lead concentrate product;

(4) adding the reduced manganese slag obtained in the step (2) into a dilute sulfuric acid solution for reaction to generate manganese sulfate mixed slurry;

(5) performing filter pressing on the manganese sulfate mixed slurry obtained in the step (4), wherein the obtained filter residue is leaching residue, and the filtrate is manganese sulfate solution;

(6) and (3) adding oxygen into the manganese sulfate solution obtained in the step (5), carrying out oxidation iron removal, filtering to obtain a pure manganese sulfate solution, directly using the pure manganese sulfate solution as an electrolytic manganese raw material, filtering to obtain iron-removed slag, and calcining at 520 ℃ to obtain a cement blending material.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.