Mine water bursting material for treating waste antimony ore as well as preparation method and application of mine water bursting material

Abstract

The invention provides a mine water bursting material for treating waste antimony ores as well as a preparation method and application of the mine water bursting material, and belongs to the technical field of wastewater treatment. The adsorption material prepared by the invention is prepared from the following raw materials in parts by weight: 30 to 50 parts of micron zero-valent iron, 2 to 4 parts of oxalic acid zero-valent iron, 0.5 to 0.7 part of mushroom sticks, 7 to 9 parts of ceramsite, 30 to 60 parts of large-particle active carbon, 80 to 120 parts of active carbon powder and 150 to 180 parts of carbonate rock. A filling reaction wall is arranged in a waste antimony ore roadway, and the filling reaction wall is composed of a lower flow guide wall, an adsorption wall, an upper flow guide wall and an adsorption wall; repeatedly arranging the filling reaction wall from the water inlet to the water outlet; then, waste antimony ore mine gushing water is guided to a roadway water inlet, waste water stays in a roadway for more than 4 days through a filling reactive barrier, and then the waste water is discharged through a water outlet; antimony dissolved in the water body is adsorbed through the adsorption effect, and the antimony element in the water is removed through precipitation; an anaerobic environment is further constructed, and release of the primary mineral antimony oxide is inhibited; the growth of microorganisms is promoted, generated sulfide reacts with soluble antimony to generate precipitates, and the antimony removal rate can reach 95% or above.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment, and in particular relates to a material for treating water gushing from abandoned antimony mines, a preparation method and application thereof. Background Art

[0002] Antimony mine wastewater is wastewater containing high concentrations of antimony generated during the mining, beneficiation and smelting of antimony mines. The antimony ions in these wastewaters are harmful to the environment and human health. Common pollutants in antimony mine wastewater mainly include antimony (Sb) and its compounds, as well as other metal and non-metal elements that coexist with antimony. These pollutants may come from waste and leakage during the mining, transportation, processing and smelting of antimony mines. Especially under acidic conditions, antimony is more likely to dissolve from the ore into the water body, forming wastewater containing high concentrations of antimony. In addition, antimony mine wastewater may also contain organic matter and inorganic salts, which may further increase the complexity of the wastewater and the difficulty of treatment.

[0003] At present, antimony mine wastewater is treated by physical treatment, chemical treatment, biological treatment and other methods. However, antimony mine wastewater is usually collected and transported to a treatment plant for treatment. Not only does the collection process cost a lot of manpower and material resources, but the existence of antimony mine wastewater over time will also pollute the local groundwater and ecological environment.

[0004] Therefore, there is an urgent need for a method for treating antimony mine wastewater in situ in antimony mines to save costs and reduce pollution. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide an anisotropic multifunctional carbon-based absorbing aerogel and a preparation method and application thereof. The material obtained by the present invention absorbs antimony dissolved in water through adsorption and precipitates to remove the antimony element in the water; further constructs an anaerobic environment to inhibit the release of native mineral antimony oxide; promotes the growth of microorganisms, and the generated sulfide reacts with the soluble antimony to produce precipitation, and can be used for abandoned tunnel filling to treat antimony-containing wastewater.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] In the first aspect, the present invention provides a material for treating water inrush in abandoned antimony mines, comprising the following raw materials in parts by weight: 30-50 parts of micronized zero-valent iron, 2-4 parts of oxalated zero-valent iron, 0.5-0.7 parts of mushroom sticks, 7-9 parts of ceramsite, 30-60 parts of large-particle activated carbon, 80-120 parts of activated carbon powder, and 150-180 parts of carbonate rock. By adopting the above technical scheme, the material obtained by the present invention has a good effect on the removal rate of antimony ions, because antimonates and arsenates can react with ferrous sulfate and ferric hydroxide to form water-insoluble precipitates, and colloidal ferric hydroxide has an adsorption effect, which can precipitate fine particles of other sulfides and oxides such as antimony, arsenic, and lead. The main reactions are as follows:

[0008] 2SbS3 3- +3FeSO4=Sb2S3↓+3FeS+3SO4 2-

[0009] 2SbO3 3- +3FeSO4=Sb2O3↓+3FeO+3SO4 2-

[0010] 4FeSO4+10H2O+O2=4H2SO4+4Fe(OH)3↓

[0011] H2SO4+Ca(OH)2=CaSO4+2H2O

[0012] Fe(OH)3+AsO3 3- =FeAsO3↓+3OH -

[0013] Fe(OH)3+SbO3 3- =FeSbO3↓+3OH -

[0014] Fe(OH)3+AsO4 3- =FeAsO4↓+3OH -

[0015] Fe(OH)3+SbO4 3- =FeSbO4↓+3OH -

[0016] At the same time, antimony salts and arsenic salts can also generate basic sulfates: As2O3.2SO3.xH2O, Sb2O3.2SO3.xH2O. These salts are difficult to dissolve in water and can be precipitated with iron hydroxide.

[0017] Preferably, the raw material particle size is 1.0×10 -2 ~30mm.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned material for treating water inrush from abandoned antimony mines, comprising the following steps:

[0019] 1) Weigh each raw material by weight;

[0020] 2) mixing the raw materials and putting them into a material bag;

[0021] 3) placing the material bag containing the raw materials in a mesh cage to form blocks.

[0022] Preferably, the volume of the material bag is less than or equal to the volume of the mesh cage.

[0023] Preferably, the pore diameter of the material bag is 0.1-0.5 mm.

[0024] Preferably, the mesh cage is a cube with a length of 500-1000 mm, a width of 500-1000 mm, and a height of 200-500 mm; the mesh area of ​​the mesh cage is 30-100 cm 2 .

[0025] Preferably, the mesh cage is a Binger mesh box, a plastic basket or a bamboo basket.

[0026] In a third aspect, the present invention provides a method for treating water inrush in an abandoned antimony mine, comprising the following steps:

[0027] 1) Tunnel filling: a filling reaction wall is set in the abandoned antimony mine tunnel, wherein the filling reaction wall is composed of a lower guide wall, an adsorption wall, an upper guide wall and an adsorption wall; the filling reaction wall is repeatedly set from the water inlet to the water outlet;

[0028] 2) Drainage treatment: The abandoned antimony mine water is guided to the tunnel inlet through the filling reaction wall to make the wastewater stay in the tunnel for more than 4 days, and then discharged through the outlet;

[0029] The adsorption wall is made by piling up the above-prepared materials for treating water inrush from abandoned antimony mines into a wall and then reinforcing it.

[0030] Preferably, the lower diversion wall is provided with a water outlet below the wall; the water outlet is 10 cm away from the tunnel ground;

[0031] The upper guide wall is provided with a water outlet above the wall; the water outlet is 10 cm away from the top of the tunnel.

[0032] Preferably, the distance between each wall among the lower guide wall, the adsorption wall, the upper guide wall and the adsorption wall is 2 to 3 m.

[0033] Contains at least the following beneficial technical effects:

[0034] 1) The material obtained by the present invention absorbs the antimony dissolved in the water through adsorption and removes the antimony element in the water by precipitation; further constructs an anaerobic environment to inhibit the release of native mineral antimony oxide; promotes the growth of microorganisms, and the generated sulfide reacts with the soluble antimony to produce precipitation.

[0035] 2) By adding diversion walls, the water flow direction can be alternating between upflow and downflow, thereby enhancing the adsorption effect of the filler; increasing the water flow path, increasing the reaction time between antimony in mine wastewater and filling materials, and promoting water purification.

[0036] 3) This material can be used for filling abandoned tunnels. During the tunnel filling stage, the precipitate generated by the reaction of the filling material and the mine wastewater can be fully utilized to block the pores in the middle of the composite filler, so that the filled material can quickly integrate with the abandoned tunnel and the ore bed. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is the cross-section of the filling reaction wall. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The term "include" or "comprising" in the present invention is an open description containing the specified components or steps described, and other specified components or steps that will not be substantially affected.

[0040] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0041] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0042] Example 1

[0043] 1) Preparation of adsorption material building blocks:

[0044] Weigh 30-50 parts of micronized zero-valent iron, 2-4 parts of oxalated zero-valent iron, 0.5-0.7 parts of mushroom sticks, 7-9 parts of ceramsite, 30-60 parts of large-particle activated carbon, 80-120 parts of activated carbon powder, and 150-180 parts of carbonate rock by weight; the particle size of the raw materials is 1.0×10 -2 ~30mm;

[0045] The raw materials are placed in a mixer and mixed evenly, and then put into a material bag with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The pore size of the material bag is 0.1-0.5mm. Then the material bag is placed in a Binger mesh cage with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The mesh area of ​​the mesh cage is 30-100cm 2 .

[0046] 2) Lane filling:

[0047] A filling reaction wall is set in the abandoned antimony mine Xinbajing tunnel, wherein the filling reaction wall is composed of a lower diversion wall, an adsorption wall, an upper diversion wall, and an adsorption wall; the filling reaction wall is repeatedly set from the water inlet to the water outlet;

[0048] The adsorption wall is made by piling the prepared materials for treating water inrush from abandoned antimony mines into a wall and reinforcing it; a water outlet is arranged under the lower diversion wall; the water outlet is 10 cm away from the tunnel ground;

[0049] The upper guide wall is provided with a water outlet above the wall; the water outlet is 10 cm away from the top of the tunnel.

[0050] 3) Drainage treatment: The water gushing out from the abandoned antimony mine is guided to the water inlet of the tunnel, and the wastewater is allowed to stay in the tunnel for 4 days through the filling reaction wall, and then discharged through the outlet.

[0051] Example 2: Water gushing control project of abandoned antimony mine (well 85) in Sandu County, Guizhou Province

[0052] 1) Preparation of adsorption material building blocks:

[0053] Weigh 30-50 parts of micronized zero-valent iron, 2-4 parts of oxalated zero-valent iron, 0.5-0.7 parts of mushroom sticks, 7-9 parts of ceramsite, 30-60 parts of large-particle activated carbon, 80-120 parts of activated carbon powder, and 150-180 parts of carbonate rock by weight; the particle size of the raw materials is 1.0×10 -2 ~30mm;

[0054] The raw materials are placed in a mixer and mixed evenly, and then put into a material bag with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The pore size of the material bag is 0.1-0.5mm. Then the material bag is placed in a Binger mesh cage with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The mesh area of ​​the mesh cage is 30-100cm 2 .

[0055] 2) Lane filling:

[0056] A filling reaction wall is set in the abandoned antimony mine Xinbajing tunnel, wherein the filling reaction wall is composed of a lower diversion wall, an adsorption wall, an upper diversion wall, and an adsorption wall; the filling reaction wall is repeatedly set from the water inlet to the water outlet;

[0057] The adsorption wall is made by piling the prepared materials for treating water inrush from abandoned antimony mines into a wall and reinforcing it; a water outlet is arranged under the lower diversion wall; the water outlet is 10 cm away from the tunnel ground;

[0058] The upper guide wall is provided with a water outlet above the wall; the water outlet is 10 cm away from the top of the tunnel.

[0059] 3) Drainage treatment: The water gushing out from the abandoned antimony mine is guided to the water inlet of the tunnel, and the wastewater is allowed to stay in the tunnel for 4 days through the filling reaction wall, and then discharged through the outlet.

[0060] Example 3 Water gushing control project of abandoned antimony mine (well 33) in Sandu County, Guizhou Province

[0061] 1) Preparation of adsorption material building blocks:

[0062] Weigh 30-50 parts of micronized zero-valent iron, 2-4 parts of oxalated zero-valent iron, 0.5-0.7 parts of mushroom sticks, 7-9 parts of ceramsite, 30-60 parts of large-particle activated carbon, 80-120 parts of activated carbon powder, and 150-180 parts of carbonate rock by weight; the particle size of the raw materials is 1.0×10 -2 ~30mm;

[0063] The raw materials are placed in a mixer and mixed evenly, and then put into a material bag with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The pore size of the material bag is 0.1-0.5mm. Then the material bag is placed in a Binger mesh cage with a length of 500-1000mm, a width of 500-1000mm, and a height of 200-500mm. The mesh area of ​​the mesh cage is 30-100cm 2 .

[0064] 2) Lane filling:

[0065] A filling reaction wall is set in the abandoned antimony mine Xinbajing tunnel, wherein the filling reaction wall is composed of a lower diversion wall, an adsorption wall, an upper diversion wall, and an adsorption wall; the filling reaction wall is repeatedly set from the water inlet to the water outlet;

[0066] The adsorption wall is made by piling the prepared materials for treating water inrush from abandoned antimony mines into a wall and reinforcing it; a water outlet is arranged under the lower diversion wall; the water outlet is 10 cm away from the tunnel ground;

[0067] The upper guide wall is provided with a water outlet above the wall; the water outlet is 10 cm away from the top of the tunnel.

[0068] 3) Drainage treatment: The water gushing out from the abandoned antimony mine is guided to the water inlet of the tunnel, and the wastewater is allowed to stay in the tunnel for 4 days through the filling reaction wall, and then discharged through the outlet.

[0069] Experimental Example 1

[0070] The antimony content of the raw wastewater and the treated wastewater in Examples 1-3 was tested, see Table 1.

[0071] Table 1 List of the effects of water treatment of antimony in abandoned antimony mines

[0072] serial number Antimony content in raw wastewater (μg / L) Antimony content after treatment (μg / L) Purification efficiency Shinyai 733～3128 103～265.34 77.35％～96.13％ Well 85 3000～15500 411.22～923.00 84.1％～95.02％ Well No. 33 3094～40000 367～3710 82.5％～95.33％

[0073] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A material for treating water inrush from abandoned antimony mines, characterized in that: The invention comprises the following raw materials in parts by weight: 30-50 parts of micronized zero-valent iron, 2-4 parts of oxalated zero-valent iron, 0.5-0.7 parts of mushroom sticks, 7-9 parts of ceramsite, 30-60 parts of large-particle activated carbon, 80-120 parts of activated carbon powder and 150-180 parts of carbonate rock.

2. The material for treating water inrush from abandoned antimony mines according to claim 1 is characterized in that: The particle size of the raw material is 1.0×10 -2 ~30mm.

3. The method for preparing the material for treating abandoned antimony mine water inrush according to claim 1, characterized in that: The following steps are involved: 1) Weigh each raw material by weight; 2) mixing the raw materials and putting them into a material bag; 3) placing the material bag containing the raw materials in a mesh cage to form blocks.

4. The preparation method according to claim 3, characterized in that: The volume of the material bag is less than or equal to the volume of the mesh cage.

5. The preparation method according to claim 3 or claim 4, characterized in that: The pore diameter of the material bag is 0.1-0.5 mm.

6. The preparation method according to claim 3 or claim 4, characterized in that: The mesh cage is a cube with a length of 500-1000 mm, a width of 500-1000 mm, and a height of 200-500 mm; the mesh area of ​​the mesh cage is 30-100 cm 2 .

7. The preparation method according to claim 3 or claim 4, characterized in that: The net cage is a Binger net box, a plastic basket or a bamboo basket.

8. A method for treating water inrush in abandoned antimony mines, characterized in that: The following steps are involved: 1) Tunnel filling: a filling reaction wall is set in the abandoned antimony mine tunnel, wherein the filling reaction wall is composed of a lower guide wall, an adsorption wall, an upper guide wall and an adsorption wall; the filling reaction wall is repeatedly set from the water inlet to the water outlet; 2) Drainage treatment: The abandoned antimony mine water is guided to the tunnel inlet through the filling reaction wall to make the wastewater stay in the tunnel for more than 4 days, and then discharged through the outlet; The adsorption wall is made by piling up the abandoned antimony mine water inrush material obtained in claim 3 into a wall and then reinforcing it.

9. The method according to claim 8, characterized in that The lower diversion wall is provided with a water outlet below the wall; the water outlet is 10 cm away from the tunnel ground; The upper guide wall is provided with a water outlet above the wall; the water outlet is 10 cm away from the top of the tunnel.

10. The method according to claim 8, characterized in that The distance between each wall among the lower guide wall, the adsorption wall, the upper guide wall and the adsorption wall is 2 to 3 meters.

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