阅读说明：本技术 一种电解锰渣湿法无害化处理方法 (Wet harmless treatment method for electrolytic manganese slag ) 是由 刘恒波 贺勇 彭云峰 彭建军 贾韶辉 陈建忠 王勇 高遇事 薛涛 于 2021-08-25 设计创作，主要内容包括：本发明属于固体废物处理技术领域,具体涉及一种电解锰渣湿法无害化处理方法；利用自然界中常见的材料或是碱性工业废渣对电解锰渣进行预处理,通过加热、提高搅拌转速和微负压工艺相结合实现电解锰渣中有害物质的充分脱除。本方法成本低、原材料易得,工艺方法简单,易控制,与传统处理方法相比,处理电解锰渣的速度大幅提高,适用于电解锰渣排放企业进行大批量处置。(The invention belongs to the technical field of solid waste treatment, and particularly relates to a wet harmless treatment method for electrolytic manganese slag; the electrolytic manganese slag is pretreated by common materials in the nature or alkaline industrial waste slag, and the harmful substances in the electrolytic manganese slag are fully removed by combining the processes of heating, improving the stirring rotating speed and micro-negative pressure. The method has the advantages of low cost, easily obtained raw materials, simple process method, easy control, and greatly improved speed of processing the electrolytic manganese slag compared with the traditional processing method, and is suitable for large-scale disposal of electrolytic manganese slag discharging enterprises.)

1. a wet harmless treatment method for electrolytic manganese slag is characterized in that the electrolytic manganese slag is crushed and ground, then water and alkaline materials are added, the water temperature and the pH value are adjusted, then stirring is carried out, the obtained mixture is fully reacted under the condition of micro negative pressure, and then solid-liquid separation and drying are carried out, thus obtaining the electrolytic manganese slag.

2. The method for the wet harmless treatment of the electrolytic manganese residues according to claim 1, wherein the alkaline materials are waste residues containing alkaline substances or natural materials.

3. The method for the wet harmless treatment of the electrolytic manganese residue according to claim 1 or 2, wherein the alkaline materials include but are not limited to quicklime, carbide slag and hydrated lime.

4. The method for the wet harmless treatment of the electrolytic manganese slag according to claim 1, wherein the solid-to-liquid ratio of the mixture is 1:1-1: 6.

5. The method for the wet harmless treatment of the electrolytic manganese residues according to claim 1, wherein the micro negative pressure condition is 40-80 kPa.

6. The method for the wet harmless treatment of the electrolytic manganese slag according to claim 1, comprising the following steps:

(1) crushing and grinding the electrolytic manganese slag, adding water and alkaline materials, adjusting the water temperature to 60-100 ℃, adjusting the solid-to-liquid ratio to 1:1-1:6, and adjusting the pH to 8-11;

(2) and (2) stirring the mixture obtained in the step (1), fully reacting for 3-10 minutes under the micro-negative pressure condition of 40-80kPa, performing solid-liquid separation, and drying at xx temperature until the water content of the electrolytic manganese slag is below 10%, thus obtaining the nontoxic electrolytic manganese slag.

7. The method as claimed in claim 6, wherein the stirring is performed at a rotation speed of 1000-3000 rpm for 3-10 min.

Technical Field

The invention belongs to the technical field of solid waste treatment, and particularly relates to a wet harmless treatment method for electrolytic manganese slag.

Background

The electrolytic manganese slag is pickling filter-press residue generated in the wet smelting production process of electrolytic manganese, is industrial solid waste discharged in the production process of metal manganese by an electrolytic manganese process, manganese ore powder reacts with sulfuric acid, a large amount of ammonia water is required to be added as a buffering agent when manganese salt solution is prepared by heating, and ammonium ions and sulfuric acid residual acid are finally discharged together in the electrolytic manganese slag and belong to acid waste residues. The electrolytic manganese slag is black and sticky, contains more than 80% of fine-grain components with particle size of less than 80 μm, and contains manganese, sulfate, ammonia nitrogen, heavy metal ions and SiO₂、MgO、K⁺、Na⁺And the like, and the treatment and the utilization are difficult. The electrolytic manganese slag is not listed in the national hazardous waste list for a moment, and belongs to the II-class general industrial solid waste. At present, the treatment method of the electrolytic manganese slag mainly adopts centralized stacking, and the leachate of the centralized stacking electrolytic manganese slag easily enters soil and underground water under the action of rainwater, so that the environment and underground water resources are polluted. 8-16t of electrolytic manganese slag is generated every 1t of electrolytic manganese is produced, according to statistics, the accumulated amount of the electrolytic manganese slag in China exceeds 1 hundred million t, and the amount of slag discharged per year exceeds 1000 million t; along with the reduction of the grade of the manganese carbonate raw ore, the discharge amount of electrolytic manganese slag is increased continuously.

The patent document with publication number CN109127650A discloses a method for harmlessly treating electrolytic manganese slag by using a cement kiln intermediate product, ammonia nitrogen in the electrolytic manganese slag is harmlessly treated by using high-temperature airflow generated in the production process of the cement kiln, alkaline materials with high CaO content and high activity, which are to be fed into the kiln in the production process of the cement, are fully stirred and reacted with the electrolytic manganese slag, the alkaline materials are dried and then aged, and waste gas containing ammonia generated in the aging process enters a mixing pipeline of an S5 system by using a micro-negative pressure of an S5 gas treatment system. The method provided by the invention has complex process, needs to intermittently extract the intermediate product of the cement kiln to influence the normal production of cement enterprises and the working condition of the kiln, also increases the energy-saving index of the cement enterprises, needs to use ammonia gas to be incapable of being completely removed in a short time (the reaction time needs about 72 hours), the micro negative pressure stated in the patent document refers to the process that the part which is not completely reacted to release the ammonia gas is continuously reacted to produce the ammonia gas in the aging process and is extracted by a fan,

the patent document with the publication number of CN102161048B discloses a harmless treatment method of electrolytic manganese slag, which comprises the steps of crushing the manganese slag, adding the crushed manganese slag into a stirrer, adding quicklime powder, water and a certain amount of silicate additives, stirring to form a uniform mixture, and recovering ammonia; adding water-soluble resin sulfonate additive and ferric oxide, stirring again, and recovering ammonia gas; fully stirring, drying, and performing landfill treatment after the inspection is qualified. The method described in this patent document aims to remove ammonia gas by adding a water reducing agent (additive of water-soluble resin sulfonate type) and a flocculant (iron oxide) to electrolytic manganese slag with ordinary stirring. However, the process is complicated, organic water reducing agent components are introduced, a small amount of soluble salt is brought in, the residue property in the treated electrolytic manganese residue is not changed (the soluble salt is more than 2%), the electrolytic manganese residue is still the type II common industrial solid waste, and the electrolytic manganese residue cannot enter a type II residue field for stockpiling. Meanwhile, the stirring time is long, secondary stirring is needed, the stirring speed is normal low-speed stirring, and the reaction temperature is normal room temperature, so that ammonia released by full reaction can be dissolved in water again, and the ammonia cannot be completely removed.

Patent document No. CN110639158B discloses a method for harmlessly treating electrolytic manganese slag, which is to stably solidify manganese and ammonia nitrogen in electrolytic manganese slag by cooperating calcium superphosphate and low-grade magnesium oxide, under the condition of weak alkali, heavy metals are mainly precipitated and stably solidified as phosphate, and ammonia nitrogen is mainly stably solidified as struvite, so that secondary pollution is not caused. According to the method disclosed by the patent, calcium superphosphate which is a rare resource material is introduced by a chemical method to remove ammonia nitrogen and solidify heavy metals, but the risk that magnesium oxide is continuously remained in electrolytic manganese slag in the form of soluble magnesium salt exists, the problem of ammonia volatilization under the condition of weak alkali cannot be thoroughly solved, the risk of secondary pollution exists, the market price of the calcium superphosphate is high, and the disposal cost is greatly increased.

Patent document No. CN109626853A discloses a harmless treatment process for electrolytic manganese slag, which comprises adding calcium hydroxide into electrolytic manganese slag to obtain a first product, adding a compound agent into a sodium chloride solution to obtain a second product, mixing the first product with the second product to obtain a third product, heating the third product, washing with hot water, filtering, and drying. Wherein the compound agent consists of citrate and aluminum sulfate. The aluminum sulfate added in the process plays a role of a flocculating agent, soluble salt is additionally introduced after the sodium chloride solution is added, the utilization difficulty of the electrolytic manganese slag is increased, and the added aluminum sulfate and the added sodium chloride belong to pure industrial raw materials, so that the cost is high, the disposal difficulty is increased, and the industrialization is difficult to implement.

Disclosure of Invention

The invention provides a method for harmless treatment of electrolytic manganese slag by a wet method, aiming at solving the problems.

The method is realized by the following technical scheme:

a wet-process method for treating the dregs of electrolytic manganese without damage includes crushing the dregs of electrolytic manganese, adding hydrated alkaline material, regulating water temp and pH value, stirring, full reaction of resultant mixture under the action of micro-negative pressure, solid-liquid separation and baking.

Further, the alkaline material is waste residue or natural material containing alkaline substances.

Further, the alkaline materials include, but are not limited to, quicklime, carbide slag, and hydrated lime.

Further, the micro negative pressure condition is 40-80 kPa.

Further, the solid-liquid ratio of the mixture is 1:1-1: 6.

Further, the drying is carried out at the drying temperature xx until the water content of the electrolytic manganese slag is below 10%.

Further, the wet harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:

(1) crushing electrolytic manganese slag, adding water and alkaline materials, and adjusting the solid-to-liquid ratio to be 1:1-1:6, adjusting the water temperature to 60-100 ℃, and adjusting the pH to 8-11;

(2) stirring at a high speed of 1000-3000 rpm for 3-10 min;

(3) fully reacting for 3-10 minutes under the condition of micro negative pressure of 40-80kPa, carrying out solid-liquid separation, and drying at xx temperature until the water content of the electrolytic manganese slag is below 10 percent, thus obtaining the nontoxic electrolytic manganese slag.

In conclusion, the beneficial effects of the invention are as follows: the method utilizes common materials in the nature or alkaline industrial waste residues to pretreat the electrolytic manganese residues, and realizes the full removal of harmful substances in the electrolytic manganese residues by combining the processes of heating, improving the stirring rotating speed and micro-negative pressure. The method has the advantages of low cost, easily obtained raw materials, simple process method and easy control, and compared with the traditional treatment method, the method does not need to add various chemical reagents and calcine at high temperature, greatly improves the speed of treating the electrolytic manganese slag, greatly reduces the energy consumption, and is suitable for large-scale treatment of electrolytic manganese slag discharging enterprises.

The invention provides a wet harmless treatment technology for harmful substances in electrolytic manganese slag aiming at the fact that electrolytic manganese slag contains ammonium sulfate, magnesium sulfate, soluble manganese, slightly soluble calcium sulfate and other heavy metal ions and based on the technical principle that the reaction rate of ammonium ions, manganese ions and magnesium ions in water is reduced along with the rise of temperature, the rise of alkalinity and the increase of stirring speed, so as to achieve the purpose of removing the harmful substances in the electrolytic manganese slag. Harmful substances in the electrolytic manganese slag can be basically removed, and the treated electrolytic manganese slag can be largely utilized in the production of cement, concrete and wall materials.

Compared with the prior art, the technical scheme of the invention has the following advantages: compared with the patent document with the publication number of CN109127650A, the method does not influence the normal working condition of waste heat providing enterprises such as cement, the ammonia gas release process is fast (3-10min), the aging treatment is not needed, the soluble manganese, magnesium and heavy metal can be effectively solidified, and meanwhile, the soluble substances such as K +, Na + and the like in the electrolytic manganese slag can be separated, and the content of soluble salts in the electrolytic manganese slag can be effectively reduced. Compared with the patent document with the publication number of CN110639158B, the invention aims to reduce the solubility of the ammonia released by the reaction in water in a short time by means of high-frequency stirring, water temperature increase, micro negative pressure and the like, and the solubility is found to be reduced to 1/10 under the room temperature condition, thereby being beneficial to the release and recovery of the ammonia. Compared with the patent document with the publication number of CN109626853A, the invention adds common quicklime or alkaline materials with high quicklime content, has lower cost, does not introduce new impurities, and only realizes the purpose of harmless treatment of electrolytic manganese slag by using an additional physical method.

Drawings

FIG. 1 is a flow chart of a process for the wet harmless treatment of electrolytic manganese slag.

Detailed Description

The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.

Example 1

A wet-process method for treating the dregs of electrolytic manganese without damage includes crushing the dregs of electrolytic manganese, adding hydrated alkaline material, regulating water temp and pH value, stirring, full reaction of resultant mixture under the action of micro-negative pressure, solid-liquid separation and baking.

Further, the alkaline material is quicklime.

Further, the wet harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:

(1) crushing electrolytic manganese slag, adding water and quicklime, adjusting the water temperature to 70 ℃, and adjusting the pH to 10;

(2) stirring at a high speed of 2000 rpm for a period of time;

(3) fully reacting for 8min under the condition of micro negative pressure of 60kPa, carrying out solid-liquid separation, drying at xx temperature, and obtaining the nontoxic electrolytic manganese slag with the water content of 8 percent.

Example 2

A wet-process method for treating the dregs of electrolytic manganese without damage includes crushing the dregs of electrolytic manganese, adding hydrated alkaline material, regulating water temp and pH value, stirring, full reaction of resultant mixture under the action of micro-negative pressure, solid-liquid separation and baking.

Further, the alkaline material is hydrated lime.

Further, the wet harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:

(1) crushing electrolytic manganese slag, adding water and slaked lime, adjusting the water temperature to 60 ℃, and adjusting the pH to 11;

(2) stirring at a high speed for 1000 rpm for a period of time;

(3) fully reacting for 10min under the condition of micro negative pressure of 60kPa, carrying out solid-liquid separation, drying at xx temperature, and obtaining the nontoxic electrolytic manganese slag with the water content of 7 percent.

Example 3

A wet-process method for treating the dregs of electrolytic manganese without damage includes crushing the dregs of electrolytic manganese, adding hydrated alkaline material, regulating water temp and pH value, stirring, full reaction of resultant mixture under the action of micro-negative pressure, solid-liquid separation and baking.

Further, the alkaline material is carbide slag.

Further, the wet harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:

(1) crushing electrolytic manganese slag, adding water and carbide slag, adjusting the water temperature to 80 ℃, and adjusting the pH to 9;

(2) stirring at a high speed of 2500 rpm for a period of time;

(3) fully reacting for 5min under the condition of micro negative pressure of 60kPa, carrying out solid-liquid separation, drying at xx temperature, and obtaining the nontoxic electrolytic manganese slag with the water content of 10 percent.

Example 4

A wet-process method for treating the dregs of electrolytic manganese without damage includes crushing the dregs of electrolytic manganese, adding hydrated alkaline material, regulating water temp and pH value, stirring, full reaction of resultant mixture under the action of micro-negative pressure, solid-liquid separation and baking.

Further, the alkaline material is red mud.

Further, the wet harmless treatment method of the electrolytic manganese slag specifically comprises the following steps:

(1) crushing electrolytic manganese slag, adding water and alkaline materials, adjusting the water temperature to 100 ℃, and adjusting the pH to 8;

(2) stirring at a high speed of 3000 r/min for a period of time;

(3) fully reacting for 3min under the condition of 80kPa of micro negative pressure, carrying out solid-liquid separation, drying at xx temperature, and obtaining the nontoxic electrolytic manganese slag with the water content of 8 percent.

The implementation effect is as follows:

after the method is implemented, a implemented sample is sent to a professional qualification institution for detection, the amount of released ammonia is detected according to GB18588-2001, the content of soluble manganese, soluble lead, soluble mercury and soluble arsenic is detected according to GB5085.3-2007, the content of magnesium oxide and alkali is detected according to GB/T176-2017, the water content is detected according to GB/T1596-2017, and the detection results are shown in the following table: