阅读说明：本技术 一种提高电解锌溶液净化产锌钴渣浸出率的方法 (Method for improving leaching rate of zinc-cobalt slag produced by purifying electrolytic zinc solution ) 是由 曾纪斌 于 2019-09-10 设计创作，主要内容包括：本发明公开了一种提高电解锌溶液净化产锌钴渣浸出率的方法。本发明采用物理和化学相结合的方法,先用物理粉碎设备将锌钴渣粉碎到48μm以下,破碎CoZn<Sub>13</Sub>(锌钴合金)外壳,然后在分散剂的存在下增大锌钴渣的酸浸反应面积,使锌钴渣在稀酸下达到90%以上的浸出。本发明相对于现有技术具有如下的优点及效果：(1)比现有工艺具有更便宜的吨处理成本；(2)设备简单、工艺安全；(3)硫酸用量较其他方法更省。(The invention discloses a method for improving leaching rate of zinc-cobalt residue produced by purifying electrolytic zinc solution. The invention adopts a method combining physics and chemistry, firstly, the zinc-cobalt slag is crushed to be below 48 mu m by physical crushing equipment, and CoZn is crushed 13 The (zinc-cobalt alloy) shell is covered, and then the acid leaching reaction area of the zinc-cobalt slag is increased in the presence of a dispersing agent, so that the zinc-cobalt slag is leached by more than 90% under dilute acid. Compared with the prior art, the invention has the following advantages and effects: (1) compared with the prior art, the method has the advantages that the ton treatment cost is lower; (2) the equipment is simple and the process is safe; (3) the usage of the sulfuric acid is more saved compared with other methods.)

1. A method for improving the leaching rate of zinc-cobalt slag produced by purifying electrolytic zinc solution is characterized by comprising the following steps:

(1) crushing zinc-cobalt slag: adding a dispersing agent into the zinc-cobalt slag with the water content of less than 5 wt% according to the weight ratio of the zinc-cobalt slag to the dispersing agent =1000: 4-12, and then crushing the zinc-cobalt slag;

(2) grading zinc-cobalt slag: grading the crushed zinc-cobalt slag to obtain zinc-cobalt slag with the particle size of less than 48 mu m;

(3) and acid leaching the zinc-cobalt slag.

2. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: the drying mode in the step (1) is drying, the temperature is 90-100 ℃, and the moisture content is measured according to GB/T8899-.

3. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: the dispersant in the step (1) is one or more of polyethylene glycol with molecular weight of 6000, sodium dodecyl benzene sulfonate or hexadecyl trimethyl ammonium bromide.

4. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: in the step (1), a dispersing agent is added according to the weight ratio of the zinc-cobalt slag to the dispersing agent =1000: 5-10.

5. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: the physical crushing equipment in the step (1) is one of a Raymond mill, a ball mill, an impact mill, a stirring mill, a vertical mill, a high-pressure roller mill, a vibration mill, a planetary mill and a jet mill.

6. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: and (3) grading is completed by adopting a mineral grader.

7. The method for improving the leaching rate of the residues generated in the purification of the electrolytic zinc solution for producing the zinc and cobalt according to claim 1, which is characterized in that: and (3) leaching zinc-cobalt slag by using dilute acid with the pH = 2.0-3.0, stirring at the speed of 200-300 rpm for 2-3 hours, and stirring at the temperature of 20-40 ℃.

8. The method for improving the leaching rate of the residues generated during the purification of the electrolytic zinc solution, according to claim 6, is characterized in that: and (4) the dilute acid in the step (3) is sulfuric acid, and the addition amount of the dilute acid is 4:1 (weight ratio) of the dilute acid to the zinc-cobalt slag.

Technical Field

The invention belongs to the technical field of comprehensive recycling of metal smelting, relates to a method for improving leaching rate of smelting slag by a wet method, and particularly relates to a method for improving leaching rate of zinc-cobalt slag produced by purifying electrolytic zinc solution.

Background

Cobalt is an important metal element. At present, the traditional fields of cobalt consumption and application mainly include battery materials, super heat-resistant alloys, tool steel, hard alloys and magnetic materials; cobalt, consumed in the form of compounds, is mainly used as catalysts, desiccants, reagents, pigments and dyes, and the like. Cobalt-60 is a widely used radioactive material, widely used in biochemistry for activation analysis; in plating, corrosion and catalysis for tracer studies; in medical treatment, it is used for radiological examination and treatment. The raw materials for producing cobalt can be divided into two categories of cobalt minerals and cobalt waste materials, wherein the cobalt waste materials are cobalt slag obtained from systems for smelting nickel, zinc and the like, or waste alloys, battery materials, catalysts and the like.

More than eighty percent of zinc is produced by a wet method all over the world, the zinc hydrometallurgy flow is zinc concentrate roasting, zinc is leached from produced roasted sand, zinc leachate is purified and decontaminated, and zinc is electrodeposited by zinc purification liquid. The zinc leachate purification and impurity removal process can generate various waste residues such as jarosite slag, lead-silver slag, copper-cadmium slag, zinc-cobalt slag and the like. Some of the waste residues are treated to different degrees (for example, lead-silver residues and copper-cadmium residues are comprehensively recovered with lead, silver, copper, zinc and other valuable elements by a wet method), but the zinc-cobalt residues and the like are not effectively treated. At present, zinc-cobalt slag generated by zinc smelting enterprises by a wet method is only subjected to simple acid washing and selective leaching. Because cobalt in the zinc-cobalt slag is mainly CoZn₁₃The zinc-cobalt alloy exists in the form, so that only a small part of metal zinc in the nickel-cobalt slag can be leached out by acid washing, a small part of zinc is recovered, the acid washing slag is stockpiled or sold at a low price, most of the sold part is purchased by small-scale zinc salt preparation enterprises, and the environment is seriously polluted when the zinc-cobalt slag is treated due to small scale, large slag amount and incomplete environmental protection facilities.

The first step of wet recovery of Zn-Co slag is to leach the Zn-Co slag into solution completely, since the Co in the Zn-Co slag is mainly CoZn₁₃The zinc particles are coated with the zinc (zinc-cobalt alloy) form, and the particle size is generally more than 5mm, so that the CoZn is difficult to be treated by the conventional wet acid leaching₁₃(Zinc-cobalt alloy) leaching into solution (CN 106119560A; Lu nationality; research on comprehensive utilization of cobalt slag [ J ]]Non-ferrous metals (smelt section), 2004(1): 501-. In order to improve the leaching rate of cobalt in the zinc-cobalt slag, the following methods are commonly used in the current industrial production: (1) firstly, the zinc-cobalt slag is treated at high temperature by a pyrogenic process and then leached by a wet process, the pretreatment method has high cost, and the leaching effect is still not ideal after the high-temperature pretreatment; (2) the pressure oxidation acid leaching method is adopted for leaching, for example, CN101550485 discloses an oxygen pressure acid leaching method for treating zinc hydrometallurgy purified waste residues), but the technology has higher treatment cost, large production consumption, large waste water amount and no advantage for treating materials with higher zinc and cobalt contents; (3) ammonia leaching process(such as CN 1310242; Zhao Tii, Tang-M, wet zinc smelting and cobalt slag purifying process [ J)]The university of China and south (Nature science edition), 2001, 32(4): 371-.

Disclosure of Invention

The invention aims to provide a method for improving the wet leaching rate of zinc-cobalt slag generated during the purification and cobalt removal of electrolytic zinc solution, which is realized by the following technical scheme: a method for improving the leaching rate of zinc-cobalt slag produced by purifying electrolytic zinc solution comprises the following steps:

(1) crushing zinc-cobalt slag: weighing the zinc-cobalt slag which is dried to the moisture content of less than 5 wt%, adding a dispersing agent according to the weight ratio of the zinc-cobalt slag to the dispersing agent =1000: 4-12, and crushing.

(2) Grading zinc-cobalt slag: and grading the crushed zinc-cobalt slag to obtain the zinc-cobalt slag with the particle size of less than 48 mu m (300 meshes).

(3) And carrying out acid leaching on the zinc-cobalt slag.

The drying mode in the step (1) is drying, the temperature is 90-100 ℃, and the moisture content is measured according to GB/T8899-.

The dispersant in the step (1) is one or more of polyethylene glycol (molecular weight 6000), sodium dodecyl benzene sulfonate or cetyl trimethyl ammonium bromide. And preferably, the dispersing agent is added according to the weight ratio of the zinc-cobalt slag to the dispersing agent =1000: 4-12.

The physical crushing equipment in the step (1) is one of a Raymond mill, a ball mill, an impact mill, a stirring mill, a vertical mill, a high-pressure roller mill, a vibration mill, a planetary mill and a jet mill.

And (3) grading by using a commercially available mineral grader.

The specific operation of the step (3) is as follows: soaking the zinc-cobalt slag by using dilute acid with the pH = 2.0-3.0, stirring at the speed of 200-300 rpm for 2-3 hours, and stirring at the temperature of 20-40 ℃. The dilute acid is sulfuric acid. The addition amount of the diluted acid is 4:1 (weight ratio) of the diluted acid to the zinc-cobalt slag, and the pH value of the diluted acid is preferably 2.0.

The present inventors studied and analyzed in detailThe characteristics and characteristics of the zinc-cobalt slag are used. Specifically, cobalt in the zinc-cobalt slag is mainly CoZn₁₃The zinc particles are coated with (zinc-cobalt alloy) form, and the particle diameter is generally more than 5mm, wherein, CoZn₁₃The thickness of the (zinc-cobalt alloy) is generally about 0.2-0.3 mm, and the metal zinc is coated inside the (zinc-cobalt alloy). Based on the above, the present invention uses a physical pulverization method to pulverize spherical zinc-cobalt slag to less than 48 μm so as to crush CoZn₁₃The (zinc-cobalt alloy) shell increases the acid leaching reaction area of the zinc-cobalt slag in the presence of a dispersant, so that the zinc-cobalt slag can be leached under dilute acid.

Thus, compared with the prior art, the invention has the following advantages and effects:

(1) the process of the present invention has a lower ton treatment cost than the prior art.

(2) The method of the invention has simple equipment and safe process.

(3) The method of the invention adopts less sulfuric acid than other methods.

(4) The method has high leaching rate of the zinc-cobalt slag, which reaches more than 90 percent.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

The process equipment or devices not specifically noted in the following examples are conventional in the art; all pressure values and ranges refer to absolute pressures.

Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.

The evaluation methods involved therein are as follows: the element content test adopts Inductively Coupled Plasma-atomic emission spectrometry (ICP-AES); the moisture test is carried out by using the GB/T6284-.