Harmless curing agent for electrolytic manganese residues and curing method of harmless curing agent

Abstract

The invention provides an electrolytic manganese residue harmless curing agent and a curing method thereof, and belongs to the technical field of industrial waste residue treatment. The harmless curing agent for the electrolytic manganese residues comprises the following raw materials in parts by weight: 40-80 parts of the electrolytic manganese residues, 30-50 parts of iron-aluminum mud, 5-15 parts of slag, 3-8 parts of kaolin, 8-12 parts of anhydrous phosphogypsum and 20-40 parts of water. The electrolytic manganese slag is solidified by adding the iron-aluminum mud, the slag, the kaolin and the anhydrous phosphogypsum, the obtained solidified body can remarkably reduce the leaching concentration of Mn < 2 + > and NH4 < + >, and the compressive strength of the manganese slag solidified body is improved.

Description

Technical Field

[0001] The invention relates to the technical field of industrial waste residue treatment, and in particular to a harmless curing agent for electrolytic manganese residue and a curing method thereof. Background Art

[0002] Electrolytic manganese slag is an industrial solid waste produced by solid-liquid separation after acid leaching of manganese ore, which contains a large amount of Mn 2+ and NH 4 + -N, electrolytic manganese slag is acidic and disperses quickly when it comes into contact with water. The soluble ions in it will be infiltrated by rainwater and decompose themselves, and quickly migrate through surface runoff or underground seepage, entering rivers, lakes and groundwater, directly polluting the water quality. Soluble ions will also migrate and transform into the soil, slowly accumulate in the soil, change the physical and chemical properties of the soil, and the accumulation of heavy metal ions will cause the heavy metal content in the soil to exceed the standard seriously.

[0003] The solidification of electrolytic manganese slag mainly involves adding a certain amount of material to the electrolytic manganese slag to effectively consolidate the heavy metals therein, thereby achieving the solidification and stabilization of heavy metal elements, thereby reducing pollution to the environment. For example, CN102161048A discloses electrolytic manganese slag treatment using quicklime powder, silicate, resin sulfonate and ferric chloride as treatment agents. CN103286116A discloses a method for harmlessly treating electrolytic manganese slag using calcium oxide and sodium phosphate as agents. In the prior art, only the concentration of manganese ion and ammonia nitrogen leaching is explored, and the strength of the electrolytic manganese slag solidified body is not involved. Therefore, it is of great significance to study a harmless solidifying agent for electrolytic manganese slag and a solidification method thereof, which can not only reduce the leaching concentration of manganese ions and ammonia nitrogen but also improve the strength of the solidified body. Summary of the invention

[0004] The object of the present invention is to provide a harmless curing agent for electrolytic manganese slag and a curing method thereof, so as to solve the problems in the prior art of high leaching concentration of manganese ions and ammonia nitrogen in the electrolytic manganese slag solidified body and low strength of the solidified body.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The invention provides a harmless curing agent for electrolytic manganese slag, which comprises the following raw materials in parts by weight: 40 to 80 parts of electrolytic manganese slag, 30 to 50 parts of iron-aluminum mud, 5 to 15 parts of slag, 3 to 8 parts of kaolin, 8 to 12 parts of anhydrous phosphogypsum and 20 to 40 parts of water.

[0007] Preferably, the electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 45-60 parts of electrolytic manganese slag, 35-45 parts of iron-aluminum mud, 8-12 parts of slag, 5-6 parts of kaolin, 9-10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

[0008] Preferably, the electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 50 parts of electrolytic manganese slag, 40 parts of iron-aluminum mud, 10 parts of slag, 5-6 parts of kaolin, 10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

[0009] Preferably, the particle size of the electrolytic manganese slag is 1 to 5 mm, preferably 1 to 3 mm, and more preferably 1 to 2 mm; the particle size of the iron-aluminum mud is 1 to 3 mm.

[0010] The present invention also provides a method for curing the electrolytic manganese slag harmless curing agent described above, comprising the following steps:

[0011] (1) mixing electrolytic manganese slag and water according to the above weight proportions to obtain a first mixed slurry;

[0012] (2) adding iron-aluminum mud and kaolin to the first mixed slurry and stirring for the first time to obtain a second mixed slurry;

[0013] (3) adding slag and anhydrous phosphogypsum to the second mixed slurry for a second stirring and solidification to obtain an electrolytic manganese slag solidified body.

[0014] Preferably, in step (1), the mixing time is 20 to 40 minutes.

[0015] Preferably, in step (2), the first stirring time is 1 to 3 hours.

[0016] Preferably, in step (3), the second stirring time is 10 to 30 minutes.

[0017] Beneficial effects of the present invention:

[0018] (1) In the present invention, ferroaluminum mud and kaolin are added to the curing agent. The ferroaluminum mud and kaolin have strong adsorption capacity for metal ions, and the manganese ions in the electrolytic manganese slag are effectively adsorbed in the ferroaluminum mud and kaolin.

[0019] (2) The present invention adds anhydrous phosphogypsum, and the slag and iron-aluminum mud react with the phosphogypsum to effectively encapsulate the manganese ions and at the same time improve the strength of the electrolytic manganese slag solid body.

[0020] (3) Adding anhydrous phosphogypsum to the curing agent of the electrolytic manganese slag of the present invention can significantly reduce the leaching concentration of manganese ions and ammonia nitrogen ions. DETAILED DESCRIPTION

[0021] The invention provides a harmless curing agent for electrolytic manganese slag, which comprises the following raw materials in parts by weight: 40 to 80 parts of electrolytic manganese slag, 30 to 50 parts of iron-aluminum mud, 5 to 15 parts of slag, 3 to 8 parts of kaolin, 8 to 12 parts of anhydrous phosphogypsum and 20 to 40 parts of water.

[0022] In the present invention, the electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 45-60 parts of electrolytic manganese slag, 35-45 parts of iron-aluminum mud, 8-12 parts of slag, 5-6 parts of kaolin, 9-10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

[0023] In the present invention, the electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 50 parts of electrolytic manganese slag, 40 parts of iron-aluminum mud, 10 parts of slag, 5-6 parts of kaolin, 10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

[0024] In the present invention, the particle size of the electrolytic manganese slag is 1 to 5 mm; the particle size of the iron-aluminum mud is 1 to 3 mm.

[0025] The present invention also provides a method for curing the electrolytic manganese slag harmless curing agent described above, comprising the following steps:

[0026] (1) mixing electrolytic manganese slag and water according to the above weight proportions to obtain a first mixed slurry;

[0027] (2) adding iron-aluminum mud and kaolin to the first mixed slurry and stirring for the first time to obtain a second mixed slurry;

[0028] (3) adding slag and anhydrous phosphogypsum to the second mixed slurry for a second stirring and solidification to obtain an electrolytic manganese slag solidified body.

[0029] In the present invention, in the step (1), the mixing time is 20 to 40 minutes, preferably 25 to 35 minutes, and more preferably 30 minutes.

[0030] In the present invention, in step (2), the first stirring time is 1 to 3 hours, preferably 1.5 to 2.5 hours, and more preferably 2 hours.

[0031] In the present invention, in step (3), the second stirring time is 10 to 30 minutes, preferably 20 minutes.

[0032] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0033] The main components and contents of the iron-aluminum mud and slag used in the embodiments of the present invention are shown in Table 1 and Table 2:

[0034] Table 1 Main components and contents of iron-aluminum mud

[0035]

[0036]

[0037] Table 2 Main components and contents of slag

[0038] Element MgO <![CDATA[Al 2 THE 3 ]]> <![CDATA[SiO 2 ]]> <![CDATA[K 2 The]]> CaO <![CDATA[Fe 2 THE 3 ]]> Content (wt%) 11.550 16.428 28.438 0.846 37.849 0.318

[0039] Example 1

[0040] Disperse 50 parts of electrolytic manganese slag (particle size range is 1-2mm) in 30 parts of water and stir for 40 minutes to obtain a first mixed slurry; add 40 parts of iron-aluminum mud (particle size range is 1-3mm) and 6 parts of kaolin to the first mixed slurry, stir for 2 hours to obtain a second mixed slurry; add 10 parts of slag and 10 parts of anhydrous phosphogypsum to the second mixed slurry, stir for 20 minutes, stir evenly and transfer it to a mold, and cure it for 12 hours to obtain an electrolytic manganese slag solidified body.

[0041] Example 2

[0042] Disperse 80 parts of electrolytic manganese slag (particle size range is 1-2mm) in 40 parts of water and stir for 30 minutes to obtain a first mixed slurry; add 30 parts of iron-aluminum mud (particle size range is 1-3mm) and 8 parts of kaolin to the first mixed slurry, stir for 3 hours to obtain a second mixed slurry; add 15 parts of slag and 12 parts of anhydrous phosphogypsum to the second mixed slurry, stir for 30 minutes, stir evenly and transfer it to a mold, cure for 12 hours to obtain an electrolytic manganese slag solidified body.

[0043] Example 3

[0044] Disperse 40 parts of electrolytic manganese slag (particle size range is 2-4 mm) in 20 parts of water and stir for 20 minutes to obtain a first mixed slurry; add 50 parts of iron-aluminum mud (particle size range is 1-3 mm) and 3 parts of kaolin to the first mixed slurry, stir for 1 hour to obtain a second mixed slurry; add 5 parts of slag and 8 parts of anhydrous phosphogypsum to the second mixed slurry, stir for 10 minutes, stir evenly and transfer it to a mold, and cure it for 12 hours to obtain an electrolytic manganese slag solidified body.

[0045] Comparative Example 1

[0046] The difference from Example 1 is that no kaolin is added, and other conditions are the same.

[0047] Comparative Example 2

[0048] The difference from Example 1 is that no slag is added, and other conditions are the same.

[0049] Comparative Example 3

[0050] The difference from Example 1 is that no anhydrous phosphogypsum is added, and other conditions are the same.

[0051] The electrolytic manganese slag solids of Examples 1 to 3 and Comparative Examples 1 to 3 were cured at room temperature for 28 days, and then leached according to the method of "HJ 557-2010" and then the leaching concentration was tested.

[0052] The electrolytic manganese slag solids of Examples 1 to 3 and Comparative Examples 1 to 3 were cured at room temperature for 28 days to conduct an unconfined compressive strength test.

[0053] The leaching concentration and unconfined compressive strength test results are shown in Table 3:

[0054] Table 3 Leaching concentration and unconfined compressive strength test results

[0055]

[0056] As can be seen from Table 3, the present invention solidifies the electrolytic manganese slag by adding iron-aluminum mud, slag, kaolin and anhydrous phosphogypsum, and the obtained solidified body can significantly reduce Mn 2+ and NH 4 + The leaching concentration is reduced and the compressive strength of the manganese slag solidification body is improved.

[0057] It can be seen from the above embodiments that the present invention provides a harmless curing agent for electrolytic manganese slag and a curing method thereof. The harmless curing agent for electrolytic manganese slag of the present invention comprises the following raw materials in parts by weight: 40 to 80 parts of electrolytic manganese slag, 30 to 50 parts of iron-aluminum mud, 5 to 15 parts of slag, 3 to 8 parts of kaolin, 8 to 12 parts of anhydrous phosphogypsum, and 20 to 40 parts of water. By adding iron-aluminum mud, slag, kaolin and anhydrous phosphogypsum to solidify the electrolytic manganese slag, the obtained solidified body can significantly reduce Mn 2+ and NH 4 + The leaching concentration is reduced and the compressive strength of the manganese slag solidification body is improved.

[0058] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A harmless curing agent for electrolytic manganese slag, characterized in that: The electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 40-80 parts of electrolytic manganese slag, 30-50 parts of iron-aluminum mud, 5-15 parts of slag, 3-8 parts of kaolin, 8-12 parts of anhydrous phosphogypsum, and 20-40 parts of water.

2. The harmless curing agent for electrolytic manganese slag according to claim 1, characterized in that: The electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 45-60 parts of electrolytic manganese slag, 35-45 parts of iron-aluminum mud, 8-12 parts of slag, 5-6 parts of kaolin, 9-10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

3. The harmless curing agent for electrolytic manganese slag according to claim 2, characterized in that: The electrolytic manganese slag harmless curing agent comprises the following raw materials in parts by weight: 50 parts of electrolytic manganese slag, 40 parts of iron-aluminum mud, 10 parts of slag, 5-6 parts of kaolin, 10 parts of anhydrous phosphogypsum, and 25-35 parts of water.

4. The harmless curing agent for electrolytic manganese slag according to any one of claims 1 to 3, characterized in that: The particle size of the electrolytic manganese slag is 1 to 5 mm; the particle size of the iron-aluminum mud is 1 to 3 mm.

5. The curing method of the electrolytic manganese slag harmless curing agent according to any one of claims 1 to 4, characterized in that: The steps include: (1) mixing electrolytic manganese slag and water according to the above weight proportions to obtain a first mixed slurry; (2) adding iron-aluminum mud and kaolin to the first mixed slurry and stirring for the first time to obtain a second mixed slurry; (3) adding slag and anhydrous phosphogypsum to the second mixed slurry for a second stirring and solidification to obtain an electrolytic manganese slag solidified body.

6. The curing method of the electrolytic manganese slag harmless curing agent according to claim 5, characterized in that: In the step (1), the mixing time is 20 to 40 minutes.

7. The curing method of the electrolytic manganese slag harmless curing agent according to claim 5 or 6, characterized in that: In the step (2), the first stirring time is 1 to 3 hours.

8. The curing method of the harmless curing agent for electrolytic manganese slag according to claim 7, characterized in that: In the step (3), the second stirring time is 10 to 30 minutes.

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