CN115108685A - Modified activated carbon carrier for in-situ treatment of mine acidic wastewater - Google Patents
Modified activated carbon carrier for in-situ treatment of mine acidic wastewater Download PDFInfo
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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Abstract
The invention discloses a modified activated carbon carrier for in-situ treatment of mine acidic wastewater, which is prepared from the following raw materials: 50-73.4% of activated carbon, 6.8-16.3% of slow-release alkaline substances, 10.2-19.6% of microbial reduction strains and 5.2-15% of microbial nutrients. The modified activated carbon carrier for in-situ treatment of mine acidic wastewater provided by the invention has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like.
Description
Technical Field
The invention relates to the technical field of mine acid wastewater treatment, in particular to a modified activated carbon carrier for in-situ treatment of mine acid wastewater.
Background
Mineral resources are the material basis for human survival and development, and 70% of industrial product raw materials and 90% of energy sources in China are both from the exploitation and utilization of the mineral resources. The mine is used as a place for mining, processing and utilizing natural resources, people can obtain beneficial mineral raw materials, meanwhile, natural landforms and environments are inevitably damaged, a large amount of solid or waste water which is difficult to recycle under the existing economic and technical conditions is generated, and the surrounding ecological environment is damaged to a certain degree. The ores are associated with various elements, a large amount of ores and mining surfaces are exposed in the environment, acidic water generated by long-term weathering leaching and waste water containing harmful heavy metal ions directly flow into a natural water system and are converged into a regional water system, and great influence and harm are caused to the production, life and ecological environment depending on the existence of downstream residents. Therefore, the control of the discharge of the acid mine wastewater is a global problem. At present, China still has a large amount of acid mine wastewater.
The acidic mine wastewater has the characteristics of strong acidity, high toxicity, concealment, long durability and great harm, the current water burst pollution events of mine pits frequently and seriously threaten the environmental quality of underground water and surface water, and the pollution prevention and control are urgent. The research on the in-situ biological treatment technology with high efficiency and low cost can pertinently solve the water burst pollution event of the mine from the aspects of mine pollution source control and process resistance control.
Disclosure of Invention
In view of the above, the invention provides a modified activated carbon carrier for in-situ treatment of mine acidic wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modified activated carbon carrier for in-situ treatment of mine acidic wastewater is prepared from the following raw materials: 50-73.4% of active carbon, 6.8-16.3% of slow-release alkaline substances, 10.2-19.6% of microbial reduction strains and 5.2-15% of microbial nutrients.
Preferably, the slow-release alkaline substance is calcium carbonate.
Preferably, the microorganism reducing bacteria is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfurizate, enterobacter desulfurizate, filarial desulfurate, monad desulfurate, bacillus desulfurate and streptococcus desulfurate; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
Preferably, the microorganism slowly releases nutrients to provide carbon source fatty acid and nitrogen source amino acid.
Preferably, the microorganism slow-release nutrient substance is corncob.
A preparation method of a modified activated carbon carrier for mine acid wastewater treatment comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonization furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; placing the black porous spherical granular carbonized material provided with the central hole into a potassium hydroxide solution with the mass fraction of 55% for soaking for 3.5h, and activating to obtain activated carbon;
s2: placing the activated carbon prepared in the step S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, performing high-temperature pyrolysis under the protection of inert gas, partially decomposing the slow-release alkaline substance calcium carbonate into calcium oxide through a firing pyrolysis effect, and filling and fixing the calcium oxide and the rest calcium carbonate on the inner surface of pores of the activated carbon to obtain modified activated carbon;
s3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to 15% of inoculation amount, inoculating in an aseptic environment, and performing sealed culture at 30 ℃ in a dark place to obtain mixed active bacterial liquid;
s4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment;
s5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product.
Preferably, the high-temperature pyrolysis temperature is 600-800 ℃.
Preferably, the inert gas is nitrogen or argon.
The modified activated carbon carrier prepared by the preparation method is used for in-situ treatment of mine acidic wastewater.
Compared with the prior art, the invention has the beneficial effects that: the modified activated carbon carrier for in-situ treatment of mine acidic wastewater provided by the invention has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like; the modified activated carbon carrier carrying the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance is injected into underground mine wastewater, firstly, the water-soluble film is melted when meeting water at normal temperature, the modified activated carbon carrier adsorbs pollutants in water to enter the inner pores, the self-carried microbial reduction strain utilizes the pollutants and the microbial nutrient substance to self-reproduce, the content of pollutants such as iron, manganese, sulfate and the like in the mine wastewater is gradually reduced, the calcium oxide and the calcium carbonate in the modified activated carbon carrier are slowly released to neutralize the acidity of the wastewater, and are combined with heavy metal ions to provide a proper PH environment for the metabolism of microorganisms, so that the environmental balance of the acidic wastewater is destroyed due to underground mining, and benign ecological balance is formed.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper," "lower," "left," "right," "inner," "outer," "front," "rear," "leading," "trailing," and the like are used in an orientation or positional relationship indicated for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1:
a modified activated carbon carrier for in-situ treatment of mine acidic wastewater is prepared from the following raw materials: 50% of activated carbon, 16% of slow-release alkaline substances, 19% of microbial reduction strains and 15% of microbial nutrients.
Wherein the slow-release alkaline substance is calcium carbonate.
The microorganism reducing strain is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfurizate, enterobacter desulfurizate, filarial desulfurate, monad desulfurate, bacillus desulfurate and streptococcus desulfurate; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
The microorganism slowly releases nutrient substances to provide carbon source fatty acid and nitrogen source amino acid; the microorganism slow-release nutrient substance is corncob.
A preparation method of a modified activated carbon carrier for mine acid wastewater treatment comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonization furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; and (3) placing the black porous spherical granular carbonized material with the central hole into 55% of potassium hydroxide solution by mass for soaking for 3.5h, and activating to obtain activated carbon. The potassium hydroxide has strong alkalinity, and the active carbon after the potassium hydroxide is adopted for activation has high adsorption capacity.
S2: placing the activated carbon prepared by S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, and carrying out high-temperature pyrolysis under the protection of inert gas, wherein the inert gas is nitrogen or argon, and the high-temperature pyrolysis temperature is 600-800 ℃; the slow-release alkaline substance calcium carbonate is partially decomposed into calcium oxide through the firing pyrolysis effect, and the calcium oxide and the rest calcium carbonate are filled and fixed on the inner surface of pores of the activated carbon to obtain the modified activated carbon.
S3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to the inoculation amount of 15%, inoculating in an aseptic environment, and placing at the temperature of 30 ℃ for dark closed culture to obtain mixed active bacterial liquid.
S4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment; the corncob can provide required nutrients for culturing the sulfate reducing bacteria, including carbon source fatty acid and nitrogen source amino acid, and the corncob is easy to obtain, easy to process, low in cost and easy to fill in the central hole of the black porous spherical granular carbonized material.
S5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product. The water-soluble film at normal temperature is sealed and wrapped in a green environment-friendly manner, so that the anaerobic environment required by sulfate reducing bacteria can be realized, and the water-soluble film at normal temperature is dissolved in water and is decomposed into water and carbon dioxide without pollution.
The modified active carbon carrier has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like. The modified activated carbon carrier carrying the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance is injected into underground mine wastewater, firstly, the water-soluble film is melted when meeting water at normal temperature, the modified activated carbon carrier adsorbs pollutants in water to enter the inner pores, the self-carried microbial reduction strain utilizes the pollutants and the microbial nutrient substance to self-reproduce, the content of pollutants such as iron, manganese, sulfate and the like in the mine wastewater is gradually reduced, the calcium oxide and the calcium carbonate in the modified activated carbon carrier are slowly released to neutralize the acidity of the wastewater, and are combined with heavy metal ions to provide a proper PH environment for the metabolism of microorganisms, so that the environmental balance of the acidic wastewater is destroyed due to underground mining, and benign ecological balance is formed.
The main functions of the Sulfate Reducing Bacteria (SRB) in removing various heavy metal ions in water are divided into three aspects: (1) s produced by SRB metabolism 2－ Can be combined with heavy metal ions (including iron, manganese, copper, zinc, septa and the like) to form insoluble sulfides, and analysis of precipitated components shows that the removal of the heavy metals in water is closely related to the result of sulfate reduction, thus proving that the SRB really precipitates the heavy metals by reducing the sulfate; (2) OH while the pH of the water body is increased － 、CO 3 2－ Concentration also increases, OH － 、CO 3 2－ Neutralizes the acidity of the water and also combines with each metal ion to form Fe (OH) 3 、Al(OH) 3 、MnCO 3 And the removal effect is achieved; (3) microorganisms secrete a variety of organic substances to form extracellular polymers containing a variety of anionic groups that can bind to heavy metal cations and ultimately be removed from water.
The modified activated carbon carrier prepared by the preparation method is used for in-situ treatment of mine acidic wastewater.
Sending the mine acidic wastewater sample 1 and the mine acidic wastewater sample 2 treated by the modified activated carbon carrier to a radio and television metering detection (Hunan) company Limited for sample sending detection (wherein sulfate SO) 4 2﹣ Detecting by using an ICS600 ion chromatograph; fe. Mn, Cu, Zn and Cd are detected by adopting an Avio 500 inductively coupled plasma emission spectrometer), and the obtained detection results are as follows:
example 2
A modified activated carbon carrier for in-situ treatment of mine acidic wastewater is prepared from the following raw materials: 60% of active carbon, 13.6% of slow-release alkaline substances, 16.2% of microbial reduction strains and 10.2% of microbial nutrients.
Wherein the slow-release alkaline substance is calcium carbonate.
The microorganism reducing strain is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfovii, enterobacter desulfurizate, hyphomycete desulfurativa, pseudomonas desulfurativa, bacillus desulfurativa and streptococcus desulfurativa; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
The microorganism slowly releases nutrient substances to provide carbon source fatty acid and nitrogen source amino acid; the microorganism slow-release nutrient substance is corncob.
A preparation method of a modified activated carbon carrier for mine acid wastewater treatment comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonization furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; and (3) placing the black porous spherical granular carbonized material with the central hole into 55% of potassium hydroxide solution by mass for soaking for 3.5h, and activating to obtain activated carbon. The potassium hydroxide has strong alkalinity, and the active carbon after the potassium hydroxide is adopted for activation has high adsorption capacity.
S2: placing the activated carbon prepared by S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, and carrying out high-temperature pyrolysis under the protection of inert gas, wherein the inert gas is nitrogen or argon, and the high-temperature pyrolysis temperature is 600-800 ℃; the slow-release alkaline substance calcium carbonate is partially decomposed into calcium oxide through the firing pyrolysis effect, and the calcium oxide and the rest calcium carbonate are filled and fixed on the inner surface of pores of the activated carbon to obtain the modified activated carbon.
S3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to the inoculation amount of 15%, inoculating in an aseptic environment, and placing at the temperature of 30 ℃ for dark closed culture to obtain mixed active bacterial liquid.
S4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment; the corncob can provide required nutrients for culturing the sulfate reducing bacteria, including carbon source fatty acid and nitrogen source amino acid, and the corncob is easy to obtain, easy to process, low in cost and easy to fill in the central hole of the black porous spherical granular carbonized material.
S5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product. The water-soluble film at normal temperature is sealed and wrapped in a green environment-friendly manner, so that the anaerobic environment required by sulfate reducing bacteria can be realized, and the water-soluble film at normal temperature is dissolved in water and is decomposed into water and carbon dioxide without pollution.
The modified active carbon carrier has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like. The modified activated carbon carrier carrying the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance is injected into underground mine wastewater, firstly, the water-soluble film is melted when meeting water at normal temperature, the modified activated carbon carrier adsorbs pollutants in water to enter the inner pores, the self-carried microbial reduction strain utilizes the pollutants and the microbial nutrient substance to self-reproduce, the content of pollutants such as iron, manganese, sulfate and the like in the mine wastewater is gradually reduced, the calcium oxide and the calcium carbonate in the modified activated carbon carrier are slowly released to neutralize the acidity of the wastewater, and are combined with heavy metal ions to provide a proper PH environment for the metabolism of microorganisms, so that the environmental balance of the acidic wastewater is destroyed due to underground mining, and benign ecological balance is formed.
The main functions of the Sulfate Reducing Bacteria (SRB) in removing various heavy metal ions in water are divided into three aspects: (1) s produced by SRB metabolism 2－ Can be combined with heavy metal ions (including iron, manganese, copper, zinc, septa and the like) to form insoluble sulfides, and analysis of precipitated components shows that the removal of the heavy metals in water is closely related to the result of sulfate reduction, thus proving that the SRB really precipitates the heavy metals by reducing the sulfate; (2) OH while the pH of the water body is increased － 、CO 3 2－ Concentration also increases, OH － 、CO 3 2－ Neutralizes the acidity of the water and also combines with each metal ion to form Fe (OH) 3 、Al(OH) 3 、MnCO 3 And the removal effect is achieved; (3) microorganisms secrete a variety of organic substances to form extracellular polymers containing a variety of anionic groups that can bind to heavy metal cations and ultimately be removed from water.
The modified activated carbon carrier prepared by the preparation method is used for in-situ treatment of mine acidic wastewater.
Sending the mine acidic wastewater sample 1 and the mine acidic wastewater sample 2 treated by the modified activated carbon carrier to a radio and television metering detection (Hunan) company Limited for sample sending detection (wherein sulfate SO) 4 2﹣ Detecting by using an ICS600 ion chromatograph; fe. Mn, Cu, Zn and Cd are detected by adopting an Avio 500 inductively coupled plasma emission spectrometer), and the obtained detection results are as follows:
example 3
A modified activated carbon carrier for in-situ treatment of mine acidic wastewater is prepared from the following raw materials: 70% of active carbon, 11.8% of slow-release alkaline substance, 10.6% of microbial reduction strain and 7.6% of microbial nutrient substance.
Wherein the slow-release alkaline substance is calcium carbonate.
The microorganism reducing strain is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfurizate, enterobacter desulfurizate, filarial desulfurate, monad desulfurate, bacillus desulfurate and streptococcus desulfurate; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
The microorganism slowly releases nutrient substances to provide carbon source fatty acid and nitrogen source amino acid; the microorganism slow-release nutrient substance is corncob.
A preparation method of a modified activated carbon carrier for mine acid wastewater treatment comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonization furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; and (3) placing the black porous spherical granular carbonized material with the central hole into 55% of potassium hydroxide solution by mass for soaking for 3.5h, and activating to obtain activated carbon. The potassium hydroxide has strong alkalinity, and the active carbon after the potassium hydroxide is adopted for activation has high adsorption capacity.
S2: placing the activated carbon prepared by S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, and carrying out high-temperature pyrolysis under the protection of inert gas, wherein the inert gas is nitrogen or argon, and the high-temperature pyrolysis temperature is 600-800 ℃; the slow-release alkaline substance calcium carbonate is partially decomposed into calcium oxide through the firing pyrolysis effect, and the calcium oxide and the rest calcium carbonate are filled and fixed on the inner surface of pores of the activated carbon to obtain the modified activated carbon.
S3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to the inoculation amount of 15%, inoculating in an aseptic environment, and placing at the temperature of 30 ℃ for dark closed culture to obtain mixed active bacterial liquid.
S4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment; the corncob can provide required nutrients for culturing the sulfate reducing bacteria, including carbon source fatty acid and nitrogen source amino acid, and the corncob is easy to obtain, easy to process, low in cost and easy to fill in the central hole of the black porous spherical granular carbonized material.
S5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product. The water-soluble film at normal temperature is sealed and wrapped in a green environment-friendly manner, so that the anaerobic environment required by sulfate reducing bacteria can be realized, and the water-soluble film at normal temperature is dissolved in water and is decomposed into water and carbon dioxide without pollution.
The modified active carbon carrier has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like. The modified activated carbon carrier carrying the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance is injected into underground mine wastewater, firstly, the water-soluble film is melted when meeting water at normal temperature, the modified activated carbon carrier adsorbs pollutants in water to enter the inner pores, the self-carried microbial reduction strain utilizes the pollutants and the microbial nutrient substance to self-reproduce, the content of pollutants such as iron, manganese, sulfate and the like in the mine wastewater is gradually reduced, the calcium oxide and the calcium carbonate in the modified activated carbon carrier are slowly released to neutralize the acidity of the wastewater, and are combined with heavy metal ions to provide a proper PH environment for the metabolism of microorganisms, so that the environmental balance of the acidic wastewater is destroyed due to underground mining, and benign ecological balance is formed.
The main functions of the Sulfate Reducing Bacteria (SRB) in removing various heavy metal ions in water are divided into three aspects: (1) s produced by SRB metabolism 2－ Can be combined with heavy metal ions (including iron, manganese, copper, zinc, septa and the like) to form insoluble sulfides, and analysis of precipitated components shows that the removal of the heavy metals in water is closely related to the result of sulfate reduction, thus proving that the SRB really precipitates the heavy metals by reducing the sulfate; (2) OH while the pH of the water body is increased － 、CO 3 2－ Concentration also increases, OH － 、CO 3 2－ Neutralizes the acidity of the water and also combines with each metal ion to form Fe (OH) 3 、Al(OH) 3 、MnCO 3 And the removal effect is achieved; (3) microorganisms secrete a variety of organic substances to form extracellular polymers, which contain a variety of anionic groups capable of binding heavy metal cations to ultimately release waterAnd (4) removing.
The modified activated carbon carrier prepared by the preparation method is used for in-situ treatment of mine acidic wastewater.
Sending the mine acidic wastewater sample 1 and the mine acidic wastewater sample 2 treated by the modified activated carbon carrier to a radio and television metering detection (Hunan) company Limited for sample sending detection (wherein sulfate SO) 4 2﹣ Detecting by using an ICS600 ion chromatograph; fe. Mn, Cu, Zn and Cd are detected by adopting an Avio 500 inductively coupled plasma emission spectrometer), and the obtained detection results are as follows:
example 4
A modified activated carbon carrier for in-situ treatment of mine acidic wastewater is prepared from the following raw materials: 73.4 percent of active carbon, 6.8 percent of slow-release alkaline substance, 14.6 percent of microbial reduction strain and 5.2 percent of microbial nutrient substance.
Wherein the slow-release alkaline substance is calcium carbonate.
The microorganism reducing strain is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfurizate, enterobacter desulfurizate, filarial desulfurate, monad desulfurate, bacillus desulfurate and streptococcus desulfurate; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
The microorganism slowly releases nutrient substances to provide carbon source fatty acid and nitrogen source amino acid; the microorganism slow-release nutrient substance is corncob.
A preparation method of a modified activated carbon carrier for mine acid wastewater treatment comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonizing furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; and (3) placing the black porous spherical granular carbonized material with the central hole into 55% of potassium hydroxide solution by mass for soaking for 3.5h, and activating to obtain activated carbon. The potassium hydroxide has strong alkalinity, and the active carbon after the potassium hydroxide is adopted for activation has high adsorption capacity.
S2: placing the activated carbon prepared by S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, and carrying out high-temperature pyrolysis under the protection of inert gas, wherein the inert gas is nitrogen or argon, and the high-temperature pyrolysis temperature is 600-800 ℃; the slow-release alkaline substance calcium carbonate is partially decomposed into calcium oxide through the firing pyrolysis effect, and the calcium oxide and the rest calcium carbonate are filled and fixed on the inner surface of pores of the activated carbon to obtain the modified activated carbon.
S3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to the inoculation amount of 15%, inoculating in an aseptic environment, and placing at the temperature of 30 ℃ for dark closed culture to obtain mixed active bacterial liquid.
S4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment; the corncob can provide required nutrients for culturing the sulfate reducing bacteria, including carbon source fatty acid and nitrogen source amino acid, and the corncob is easy to obtain, easy to process, low in cost and easy to fill in the central hole of the black porous spherical granular carbonized material.
S5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product. The water-soluble film at normal temperature is sealed and wrapped in a green environment-friendly manner, so that the anaerobic environment required by sulfate reducing bacteria can be realized, and the water-soluble film at normal temperature is dissolved in water and is decomposed into water and carbon dioxide without pollution.
The modified active carbon carrier has the advantages of developed void structure, large specific surface area, strong adsorption capacity, rich alkaline substances, slow release, small bed resistance, good chemical stability, easy regeneration, durability and the like. The modified activated carbon carrier carrying the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance is injected into underground mine wastewater, firstly, the water-soluble film is melted when meeting water at normal temperature, the modified activated carbon carrier adsorbs pollutants in water to enter the inner pores, the self-carried microbial reduction strain utilizes the pollutants and the microbial nutrient substance to self-reproduce, the content of pollutants such as iron, manganese, sulfate and the like in the mine wastewater is gradually reduced, the calcium oxide and the calcium carbonate in the modified activated carbon carrier are slowly released to neutralize the acidity of the wastewater, and are combined with heavy metal ions to provide a proper PH environment for the metabolism of microorganisms, so that the environmental balance of the acidic wastewater is destroyed due to underground mining, and benign ecological balance is formed.
The main functions of the Sulfate Reducing Bacteria (SRB) in removing various heavy metal ions in water are divided into three aspects: (1) s produced by SRB metabolism 2－ Can be combined with heavy metal ions (including iron, manganese, copper, zinc, septa and the like) to form insoluble sulfides, and analysis of precipitated components shows that the removal of the heavy metals in water is closely related to the result of sulfate reduction, thus proving that the SRB really precipitates the heavy metals by reducing the sulfate; (2) OH while the pH of the water body is increased － 、CO 3 2－ Concentration also increases, OH － 、CO 3 2－ Neutralizes the acidity of the water and also combines with each metal ion to form Fe (OH) 3 、Al(OH) 3 、MnCO 3 And the removal effect is achieved; (3) microorganisms secrete a variety of organic substances to form extracellular polymers, which contain a variety of anionic groups capable of binding heavy metal cations to eventually pass throughAnd (4) removing the water.
The modified activated carbon carrier prepared by the preparation method is used for in-situ treatment of mine acidic wastewater.
Sending the mine acidic wastewater sample 1 and the mine acidic wastewater sample 2 treated by the modified activated carbon carrier to a radio and television metering detection (Hunan) company Limited for sample sending detection (wherein sulfate SO) 4 2﹣ Detecting by using an ICS600 ion chromatograph; fe. Mn, Cu, Zn and Cd are detected by adopting an Avio 500 inductively coupled plasma emission spectrometer), and the obtained detection results are as follows:
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. A modified activated carbon carrier for in-situ treatment of mine acidic wastewater is characterized by comprising the following raw materials: 50-73.4% of active carbon, 6.8-16.3% of slow-release alkaline substances, 10.2-19.6% of microbial reduction strains and 5.2-15% of microbial nutrients.
2. The modified activated carbon carrier for in-situ treatment of mine acidic wastewater according to claim 1, wherein the slow-release alkaline substance is calcium carbonate.
3. The modified activated carbon carrier for in-situ treatment of mine acidic wastewater according to claim 1, wherein the microorganism reducing bacteria is sulfate reducing bacteria; the sulfate reducing bacteria is a mixed solution consisting of vibrio desulfurizate, enterobacter desulfurizate, filarial desulfurate, monad desulfurate, bacillus desulfurate and streptococcus desulfurate; wherein the content of the vibrio desulfurizate accounts for 80-90% of the total amount of the microbial reducing strain, and the common content of the enterobacter desulfurizate, the filamentium desulfurizate, the monad desulfurizate, the bacillus desulfurizate and the streptococcus desulfurizate accounts for 10-20% of the total amount of the microbial reducing strain.
4. The modified activated carbon carrier for in-situ treatment of mine acidic wastewater as claimed in claim 1, wherein the microorganism slow-release nutrient substance provides carbon source fatty acid and nitrogen source amino acid.
5. The modified activated carbon carrier for in-situ treatment of mine acidic wastewater as claimed in claim 4, wherein the microorganism slow-release nutrient substance is corncob.
6. A preparation method of the modified activated carbon carrier for the treatment of the acid mine wastewater as claimed in any one of claims 1 to 5, which comprises the following steps:
s1: mixing high-quality anthracite, nut shells and a binder, kneading, crushing, extruding and forming the mixture, and drying to obtain a mixture; carbonizing the mixture in a carbonization furnace to obtain a carbonized material, and placing the carbonized material in a spherical particle forming device to obtain a plurality of black porous spherical granular carbonized materials with central holes; placing the black porous spherical granular carbonized material provided with the central hole into a potassium hydroxide solution with the mass fraction of 55% for soaking for 3.5h, and activating to obtain activated carbon;
s2: placing the activated carbon prepared in the step S1 in a pyrolysis reaction device, adding a slow-release alkaline substance calcium carbonate, carrying out high-temperature pyrolysis under the protection of inert gas, partially decomposing the slow-release alkaline substance calcium carbonate into calcium oxide through a firing pyrolysis effect, and filling and fixing the calcium oxide and the rest part of calcium carbonate on the inner surface of pores of the activated carbon to obtain modified activated carbon;
s3: inoculating sulfate reducing bacteria into sterilized Postage C enrichment culture medium liquid in an anaerobic box according to 15% of inoculation amount, inoculating in an aseptic environment, and performing sealed culture at 30 ℃ in a dark place to obtain mixed active bacterial liquid;
s4: inoculating the mixed active bacterial liquid prepared in the step S3 to a microbial nutrient substance corncob to enable various microbial strains to be attached to the surface of the corncob and form a biological membrane, and embedding and filling the corncob full of sulfate reducing bacteria into a central hole of a black porous spherical granular carbonized material in an anaerobic environment;
s5: and (4) sealing and wrapping the modified activated carbon attached with the microbial reduction strain, the slow-release alkaline substance, the calcium oxide and the microbial nutrient substance obtained in the step (S4) in an anaerobic environment by adopting a green environment-friendly normal-temperature water-soluble film to obtain a final modified activated carbon carrier finished product.
7. The preparation method of the modified activated carbon carrier for the treatment of the acid mine wastewater according to claim 6, wherein the high-temperature pyrolysis temperature is 600-800 ℃.
8. The preparation method of the modified activated carbon carrier for the treatment of the acid mine wastewater according to claim 6, wherein the inert gas is nitrogen or argon.
9. Use of the modified activated carbon support prepared according to the method of claim 6, wherein the modified activated carbon support is used for in situ treatment of mine acidic wastewater.
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