CN109626647B - Industrial heavy metal sewage treatment method based on flocculation flotation precipitation - Google Patents
Industrial heavy metal sewage treatment method based on flocculation flotation precipitation Download PDFInfo
- Publication number
- CN109626647B CN109626647B CN201910010691.6A CN201910010691A CN109626647B CN 109626647 B CN109626647 B CN 109626647B CN 201910010691 A CN201910010691 A CN 201910010691A CN 109626647 B CN109626647 B CN 109626647B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- heavy metal
- fiber bundle
- parts
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to the technical field of water pollution treatment, in particular to a flocculation flotation precipitation-based industrial heavy metal sewage treatment method, which comprises an aeration treatment step, a pH value adjustment step, a flocculation step, an air flotation step and a precipitation filtration step. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation takes water hyacinth plants as raw materials, has low cost, can effectively treat heavy metal ions in sewage, does not produce secondary pollution, and has stable treatment effect.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a flocculation flotation precipitation-based industrial heavy metal sewage treatment method.
Background
In recent years, along with the rapid development of industry and the lag of sewage treatment technology and the lack of consciousness on sewage treatment, a lot of sewage is discharged at will, so that serious environmental pollution and water resource waste are caused, and discharged industrial wastewater often contains more or less heavy metals.
Heavy metal wastewater is wastewater with the characteristics of strong toxicity, carcinogenicity, mutagenicity, difficult degradation, easy enrichment and the like, has the characteristics of toxicity effect, long-term persistence, biodegradability and the like, heavy metal is dissolved in the wastewater or suspended in the wastewater, cannot be degraded by microorganisms, can only migrate and convert among water, substrate and organisms in different valence states to generate dispersion and enrichment effects, and the heavy metal in the water body accumulated to a certain limit can generate serious harm to the water body, aquatic plants and aquatic animal systems, so that organisms have vicious symptoms, physiological obstruction, growth retardation and even death, the structure and function of the whole aquatic ecosystem are damaged and collapsed, and simultaneously, the heavy metal can enter a human body through the action of food chains and be accumulated in the human body, thereby causing various diseases and functional disorders and finally causing serious harm to the health of the human body, with the development of industry, heavy metal pollution is also widely regarded.
The existing sewage treatment technologies can be divided into physical methods, chemical methods, physicochemical methods and biological methods according to the principle, wherein the physical methods are used for separating and recovering insoluble pollutants in a suspended state in the wastewater through physical action, and the gravity separation method, the centrifugal separation method, the filtration method and the like are commonly used. The chemical treatment method is to add certain chemical substances into the sewage, separate and recover the pollutants in the sewage by utilizing chemical reaction, and the chemical precipitation method, the coagulation method, the neutralization method, the oxidation-reduction method and the like are commonly used; the physical and chemical method is to remove pollutants in the wastewater by utilizing the physical and chemical action, and mainly comprises an adsorption method, an ion exchange method, a membrane separation method, an extraction method and the like; the biological treatment method is a method for converting organic pollutants in a solution, colloid and fine suspension state in wastewater into stable and harmless substances by the metabolism of microorganisms, and can be divided into an aerobic biological treatment method and an anaerobic biological treatment method.
However, these methods have the disadvantages of unstable removal effect, easy generation of secondary pollution, high treatment cost, etc., so how to select a reasonable, effective and practical method for removing heavy metal ions is a problem that is generally faced at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a flocculation flotation precipitation-based industrial heavy metal sewage treatment method, wherein water hyacinth is used as a raw material to prepare a flocculant, the cost is low, heavy metal ions in sewage are treated, secondary pollution is not generated, and the treatment effect is stable.
The invention solves the technical problems by the following technical means:
the industrial heavy metal sewage treatment method based on the flocculation flotation precipitation comprises the following steps:
aeration treatment: discharging the sewage into an aeration tank, and spraying O from the bottom of the aeration tank through a nano aeration head3Carrying out aeration treatment on the gas for 3-4 h;
adjusting the pH value: discharging the sewage subjected to aeration treatment into a regulating tank, adding a sodium carbonate/sodium bicarbonate buffer solution into the regulating tank, and regulating the pH value to 6-7;
flocculation: discharging the sewage subjected to pH value adjustment treatment into a sewage treatment tank, adding a flocculating agent into the sewage treatment tank, stirring at the speed of 300rpm for 5min, and standing for 2 h;
air flotation: placing the flocculated sewage into a flotation column for flotation;
precipitation and filtration: and (4) placing the sewage subjected to flotation in a sedimentation tank, and standing for sedimentation.
According to the sewage treatment method, substances in the sewage are oxidized through aeration treatment so as to facilitate subsequent treatment, the pH value of the sewage is adjusted to a slightly acidic environment, a flocculating agent is favorable to better exert a flocculation effect, heavy metal in the sewage is coagulated, and finally heavy metal agglomerates are coagulated through air floatation and precipitation steps to be removed so as to achieve the purpose of purifying the industrial heavy metal sewage.
Further, the flocculating agent used in the flocculation step comprises the following raw materials in parts by weight: 20-30 parts of modified water hyacinth air bag fiber bundle pipe, 1-2 parts of calcium hypochlorite, 0.1-0.5 part of polyaluminum ferric chloride, 15-20 parts of nano zinc oxide/carbon quantum dot complexing agent, 5-10 parts of sepiolite, 10-15 parts of activated carbon and 5-10 parts of zeolite.
Further, the flocculant comprises the following raw materials in parts by weight: 25 parts of modified water hyacinth air bag fiber bundle tube, 1.5 parts of calcium hypochlorite, 0.4 part of polyaluminum ferric chloride, 15 parts of nano zinc oxide/carbon quantum dot complexing agent, 8 parts of sepiolite, 14 parts of activated carbon and 9 parts of zeolite.
Further, the preparation method of the flocculant comprises the following steps: respectively weighing a modified water hyacinth air bag fiber bundle tube and a nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring for 30min at the speed of 100rpm, uniformly mixing to obtain a mixture A, adding polyaluminum ferric chloride into a ball mill, ball-milling for 3h at the speed of 300-350 rpm, adding sepiolite and zeolite, ball-milling for 2h at the speed of 200-300 rpm, finally adding activated carbon and an adhesive, ball-milling for 1h at the speed of 100-120 rpm to obtain a mixture B, adding the mixture A into the mixture B, adding calcium hypochlorite, performing ultrasonic oscillation and cooling, uniformly mixing, placing the mixed material into a drying oven, drying at the constant temperature of 65-75 ℃ for 10-15 min to obtain flocculant powder, and sealing and storing in a dry shade.
Through the combination of the modified water hyacinth air bag fibers and the nano zinc oxide/carbon quantum dots, the flocculation precipitation of heavy metal ions in industrial heavy metal sewage can be realized, and meanwhile, organic substances in the sewage can be decomposed, so that the organic substances are prevented from being wrapped by a flocculating agent, and the flocculation effect is reduced; in addition, polyaluminum ferric chloride, calcium hypochlorite and active carbon are added into the flocculating agent, so that a certain adsorption and sterilization effect is achieved, the particle sizes of all substances can be matched more and the combination is more uniform through graded ball milling, and the substances are compounded onto the modified water hyacinth air bag fiber bundle tube as raw materials, so that the adsorption effect of the modified water hyacinth air bag fiber bundle tube can be increased, and the flocculation effect is improved; in addition, the added zeolite and the sepiolite can be used as a supporting aggregate on one hand, and on the other hand, the weight of the flocculant can be increased, meanwhile, the sepiolite can absorb water in the using process, the weight is further increased, and the flocculant can be prevented from floating on the water surface in the using process, so that the flocculation effect is reduced.
Further, the modified water hyacinth air sac fiber bundle tube is prepared by pretreating healthy water hyacinth plants, adding 0.5-1.0 wt% of modified shell powder, uniformly mixing to obtain an air sac fiber bundle tube, mixing the air sac fiber bundle tube with equal mass of polyaluminum ferric chloride to obtain a solid mixture, heating the solid mixture to 70-75 ℃ by far infrared, stirring in the heating process, simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.05-0.2% of the mass of the air sac fiber bundle tube, and continuously stirring for 5-10min after spraying to obtain the modified water hyacinth air sac fiber bundle tube.
The modified shell powder is adopted to compound the water hyacinth air bag fiber bundle tube, the modified shell powder has stronger adsorption performance, so the adsorption performance of the water hyacinth air bag fiber bundle tube can be increased to a certain extent, the flocculation effect of the water hyacinth air bag fiber bundle tube is increased, the chitosan acetic acid solution is sprayed in the process of far infrared heating, the chitosan molecule has free amino and has the performance of a cation flocculation purifying agent in an acid solution, under the condition of infrared oxidation, on one hand, the air bag fiber bundle tube can be fully combined with polymeric aluminum ferric chloride, heavy metal ions in sewage are rapidly permeated and absorbed by the flocculation purifying agent through the capillary action, the heavy metal removal effect is improved, on the other hand, in the spraying process, the chitosan acetic acid solution is uniformly dispersed on the surface of a solid mixture, under the infrared heating condition, acetic acid is evaporated, and chitosan is separated out, the modified shell powder and the air bag fiber bundle tube are compounded on the air bag fiber bundle tube, and meanwhile, a certain connecting effect is achieved between the modified shell powder and the air bag fiber bundle tube, so that the two are combined more tightly.
Further, the pretreatment comprises the steps of taking water hyacinth healthy plants with the average diameter of 2.5-4.5 cm at the air sac part, cutting the plants to obtain the air sac and plant stems with the diameters of 0.5-1 cm above and below the air sac, drying in vacuum until the moisture content of the plant stems is 20% -30%, stripping the surface layer, cutting the stripped surface layer, and sieving with a 30-mesh sieve.
Further, the modified shell powder is prepared by pickling shells, calcining at 700 ℃, and crushing by using a nano crusher.
Organic matters and impurities on the outer surface of the shell can be removed through acid washing, and a plurality of fine micropores are distributed on the shell after the shell is calcined at the temperature of 700 ℃, so that the adsorption capacity of the shell powder is further improved.
Further, the preparation method of the nano zinc oxide/carbon quantum dot complexing agent comprises the following steps: weighing barium stearate and unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid in a reaction kettle, heating to 25-35 ℃, adding a surfactant, deionized water and a defoaming agent, dispersing at 60-80 ℃ and 500rpm for 20-30 min, cooling to room temperature, adding nano zinc oxide powder, deionized water and a dispersing agent, heating in a water bath to 25-30 ℃, dispersing at 200-300 rpm for 40-60 min to obtain nano zinc oxide dispersion liquid, adding a carbon quantum dot solution into the zinc oxide dispersion liquid, stirring and mixing, placing the mixed liquid in a high-pressure reaction kettle, reacting at 80-100 ℃ for 3-5 h, cooling to room temperature, washing, centrifuging and drying a product to obtain the nano zinc oxide/carbon quantum dot composite agent.
Barium stearate is used as a dispersion liquid, so that the nano zinc oxide dispersion liquid is dispersed more uniformly, and meanwhile, the added surfactant reduces the interfacial tension between two phases and reduces the agglomeration of particles.
Furthermore, the nano zinc oxide is in a three-dimensional flower-shaped structure, and the specific surface area is 1000-1200 square meters per gram. The three-dimensional flower-like structure has larger specific surface area, more contact points with carbon quantum dots and tighter combination.
Further, the mass ratio of the barium stearate to the unsaturated fatty acid is 1: 2.
the invention has the beneficial effects that:
(1) according to the invention, the wastewater containing heavy metal ions is treated through the aeration treatment step, the pH value adjustment step, the flocculation step, the air flotation step and the precipitation filtration step, so that the treatment effect is stable, and no secondary pollution is generated.
(2) The flocculating agent used in the flocculating agent step adopts water hyacinth plants as raw materials, on one hand, the cost is lower, on the other hand, the problem of water area pollution caused by excessive propagation of the existing domestic water hyacinth can be solved to a certain extent, and meanwhile, the water hyacinth air bag fiber bundle pipe is modified by adopting modified shell powder and chitosan, so that the water hyacinth air bag fiber bundle pipe is fully combined with polyaluminium ferric chloride, and the heavy metal removal effect is improved to a certain extent.
(3) The nano zinc oxide/carbon quantum dot complexing agent has good dispersibility, zinc oxide has a photocatalysis effect, organic pollutants in sewage can be decomposed under the condition of illumination adjustment, the flocculation effect on heavy metals can be further enhanced, organic matters can be decomposed under the condition of illumination, the organic matters are prevented from wrapping a flocculating agent, the flocculation effect is influenced, and the purification effect of the heavy metal sewage is further improved.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
the preparation method of the flocculant used in the industrial heavy metal sewage treatment method based on flocculation flotation precipitation comprises the following steps:
example one
Preparation of modified shell powder: cleaning shells, drying at 60 ℃, adding 0.1mol/L nitric acid solution, carrying out reflux reaction at 75 ℃ for 2h, taking out the shells after the reaction is finished, washing to be neutral by deionized water, airing, placing in a calcining furnace, heating to 700 ℃, calcining for 4h, cooling to room temperature along with the furnace, taking out, and crushing by a nano crusher to obtain the modified shell powder.
Preparing a chitosan acetic acid solution: weighing 2g of chitosan, adding 100mL of water, adding 2mL of glacial acetic acid, stirring uniformly, heating to 85 ℃, adding water to a constant volume of 100mL, and keeping the temperature for 45min to obtain a 1% chitosan acetic acid solution.
Preparing a modified water hyacinth air bag fiber bundle tube: taking a water hyacinth healthy plant with the average diameter of 2.5-4.5 cm at the air sac part, cutting to obtain an air sac and plant stems with the length of 0.5cm above and below the air sac, performing vacuum drying until the moisture content of the plant stems is about 20%, stripping off the surface layer, then peeling off the surface layer, shearing, sieving with a 30-mesh sieve, adding 0.5% by weight of modified shell powder, uniformly mixing to obtain an air sac fiber bundle pipe, taking the air sac fiber bundle pipe, mixing with equal mass of polyaluminum ferric chloride to obtain a solid mixture, performing far infrared heating on the solid mixture to 75 ℃, stirring in the heating process, and simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.05% of the mass of the air sac fiber bundle pipe, and after spraying, continuing stirring for 5min to obtain the modified water hyacinth air sac fiber bundle pipe.
Preparing a nano zinc oxide/carbon quantum dot complexing agent: weighing 5kg of barium stearate and 10kg of unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid into a reaction kettle, heating the mixture to 25 ℃, then adding 0.1kg of surfactant, 5kg of deionized water and 0.01kg of defoaming agent, dispersing the mixture for 30min at 60 ℃ and 500rpm, cooling the mixture to room temperature, then adding 10kg of three-dimensional flower-shaped nano zinc oxide powder, 5kg of deionized water and 0.2kg of dispersing agent, heating the mixture in a water bath to 30 ℃, dispersing the mixture for 60min at 200rpm to obtain nano zinc oxide dispersion liquid, adding 5kg of carbon quantum dot solution into the zinc oxide dispersion liquid, stirring and mixing the mixture, placing the mixed liquid into a high-pressure reaction kettle, reacting the mixture for 5h at 80 ℃, cooling the mixture to room temperature, washing, centrifuging and drying the product to obtain the nano zinc oxide/carbon quantum dot composite agent.
Preparing a flocculating agent: respectively weighing 20kg of modified water hyacinth air bag fiber bundle tube and 20kg of nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring for 30min at the speed of 100rpm, uniformly mixing to obtain a mixture A, then adding 0.1kg of polyaluminum ferric chloride into a ball mill, ball-milling for 3h at the speed of 300rpm, then adding 10kg of sepiolite and 5kg of zeolite, ball-milling for 2h at the speed of 250rpm, finally adding 10kg of active carbon and 0.1kg of adhesive, ball-milling for 1h at the speed of 100rpm to obtain a mixture B, adding the mixture A into the mixture B, then adding 1kg of calcium hypochlorite, carrying out ultrasonic oscillation and uniform mixing under the conditions of 30kHz and 120W, placing the mixed material into a drying oven, drying at the constant temperature of 65 ℃ for 15min to obtain flocculant powder, and sealing and storing in a dry and cool place.
The application of the prepared flocculant powder in sewage treatment is as follows:
aeration treatment: sewage is discharged into an aeration tank, a plurality of nano aeration heads are arranged at the bottom of the aeration tank, and O is sprayed out from the bottom of the aeration tank through the nano aeration heads3Gas, a single nanometer aeration head sprays out O according to the flow of 3L/min3Carrying out aeration treatment on the gas for 3-4 h;
adjusting the pH value: discharging the sewage subjected to aeration treatment into a regulating tank, adding a sodium carbonate/sodium bicarbonate buffer solution into the regulating tank, and regulating the pH value to 6-7;
flocculation: discharging the sewage subjected to pH value adjustment treatment into a sewage treatment tank, and adding the sewage into the sewage treatment tank according to the concentration of 1kg/m3Adding the flocculant according to the amount of the active components, stirring for 5min at the speed of 300rpm, and standing for 2 h;
air flotation: placing the flocculated sewage into a flotation column for flotation, generating rotational flow through tangential water inflow, and simultaneously fully mixing the inflow water with dissolved air water with the circulation amount being 2-3 times of the inflow water amount to ensure that micro bubbles in the water are fully contacted with suspended particles, and carrying the suspended particles to a flotation tank at the upper part of the column for discharge through a static buoyancy section of the flotation column;
precipitation and filtration: and (3) placing the sewage subjected to flotation in a sedimentation tank, standing and precipitating for 24h to further agglomerate and precipitate suspended particles remained in the sewage so as to achieve the purpose of fully removing the suspended particles.
Example two
The preparation of the modified shell powder was the same as in example one.
The chitosan acetic acid solution was prepared as in example one.
Preparing a modified water hyacinth air bag fiber bundle tube: taking a water hyacinth healthy plant with the average diameter of 2.5-4.5 cm at the air sac part, cutting to obtain an air sac and plant stems with the length of 0.5cm above and below the air sac, performing vacuum drying until the moisture content of the plant stems is about 25%, stripping off the surface layer, then peeling off the surface layer, shearing, sieving with a 30-mesh sieve, adding 0.8% by weight of modified shell powder, uniformly mixing to obtain an air sac fiber bundle pipe, taking the air sac fiber bundle pipe, mixing with equal mass of polyaluminum ferric chloride to obtain a solid mixture, performing far infrared heating on the solid mixture to 70 ℃, stirring in the heating process, and simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.18% of the mass of the air sac fiber bundle pipe, and continuing stirring for 10min after spraying is finished to obtain the modified water hyacinth air sac fiber bundle pipe.
Preparing a nano zinc oxide/carbon quantum dot complexing agent: weighing 5kg of barium stearate and 10kg of unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid into a reaction kettle, heating the barium stearate and the unsaturated fatty acid to 28 ℃, then adding 0.1kg of surfactant, 5kg of deionized water and 0.01kg of defoaming agent, dispersing the barium stearate and the deionized water at 70 ℃ and 500rpm for 25min, cooling the mixture to room temperature, then adding 10kg of three-dimensional flower-shaped nano zinc oxide powder, 5kg of deionized water and 0.2kg of dispersing agent, heating the mixture in a water bath to 25 ℃, dispersing the mixture at 300rpm for 50min to obtain nano zinc oxide dispersion liquid, adding 5kg of carbon quantum dot solution into the zinc oxide dispersion liquid, stirring and mixing the mixture, placing the mixture into a high-pressure reaction kettle, reacting the mixture at 85 ℃ for 4h, cooling the mixture to room temperature, washing, centrifuging and drying the product to obtain the nano zinc oxide/carbon quantum dot composite agent.
Preparing a flocculating agent: respectively weighing 20kg of modified water hyacinth air bag fiber bundle tube and 15kg of nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring the mixture for 30min at the speed of 100rpm, uniformly mixing the mixture to obtain a mixture A, then adding 0.5kg of polyaluminum ferric chloride into a ball mill, carrying out ball milling for 3h at the speed of 325rpm, then adding 5kg of sepiolite and 10kg of zeolite, carrying out ball milling for 2h at the speed of 200rpm, finally adding 12kg of active carbon and 0.1kg of adhesive, carrying out ball milling for 1h at the speed of 110rpm to obtain a mixture B, adding the mixture A into the mixture B, then adding 1.5kg of calcium hypochlorite, carrying out ultrasonic oscillation and uniform mixing under the conditions of 30kHz and 120W, placing the mixed material into a drying oven, drying the mixed material for 15min at the constant temperature of 70 ℃ to obtain flocculant powder, and sealing and storing the flocculant powder in a dry and cool place.
The application method of the flocculant powder prepared in the embodiment in sewage treatment is the same as that in the embodiment I.
EXAMPLE III
The preparation of the modified shell powder was the same as in example one.
The chitosan acetic acid solution was prepared as in example one.
Preparing a modified water hyacinth air bag fiber bundle tube: taking a water hyacinth healthy plant with the average diameter of 2.5-4.5 cm at the air sac part, cutting to obtain an air sac and plant stems with the length of 1cm above and below the air sac, carrying out vacuum drying until the moisture content of the plant stems is about 20%, stripping off the surface layer, then shearing the stripped surface layer, sieving with a 30-mesh sieve, adding 0.15% by weight of modified shell powder, mixing uniformly to obtain an air sac fiber bundle tube, taking the air sac fiber bundle tube, mixing with polymeric aluminum ferric chloride with equal mass to obtain a solid mixture, carrying out far infrared heating on the solid mixture to 72 ℃, stirring in the heating process, and simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.10% of the mass of the air sac fiber bundle tube, and continuing stirring for 8min after spraying is finished to obtain the modified water hyacinth air sac fiber bundle tube.
Preparing a nano zinc oxide/carbon quantum dot complexing agent: weighing 5kg of barium stearate and 10kg of unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid into a reaction kettle, heating the barium stearate and the unsaturated fatty acid to 35 ℃, then adding 0.1kg of surfactant, 5kg of deionized water and 0.01kg of defoaming agent, dispersing the barium stearate and the deionized water at 80 ℃ and 500rpm for 20min, cooling the mixture to room temperature, then adding 10kg of three-dimensional flower-shaped nano zinc oxide powder, 5kg of deionized water and 0.2kg of dispersing agent, heating the mixture in a water bath to 25 ℃, dispersing the mixture at 250rpm for 40min to obtain nano zinc oxide dispersion, adding 5kg of carbon quantum dot solution into the zinc oxide dispersion, stirring and mixing the mixture, placing the mixture into a high-pressure reaction kettle, reacting the mixture at 100 ℃ for 3h, cooling the mixture to room temperature, washing, centrifuging and drying the product to obtain the nano zinc oxide/carbon quantum dot composite agent.
Preparing a flocculating agent: respectively weighing 30kg of modified water hyacinth air bag fiber bundle tube and 18kg of nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring for 30min at the speed of 100rpm, uniformly mixing to obtain a mixture A, then adding 0.3kg of polyaluminum ferric chloride into a ball mill, ball-milling for 3h at the speed of 350rpm, then adding 6kg of sepiolite and 10kg of zeolite, ball-milling for 2h at the speed of 300rpm, finally adding 15kg of active carbon and 0.1kg of adhesive, ball-milling for 1h at the speed of 120rpm to obtain a mixture B, adding the mixture A into the mixture B, then adding 2kg of calcium, carrying out ultrasonic oscillation and uniform mixing under the conditions of 30kHz and 120W, placing the mixed material into a baking oven, drying at the constant temperature of 75 ℃ for 13min to obtain flocculant powder, and sealing and storing in a dry and cool place.
The application method of the flocculant powder prepared in the embodiment in sewage treatment is the same as that in the embodiment I.
Example four
The preparation of the modified shell powder was the same as in example one.
The chitosan acetic acid solution was prepared as in example one.
Preparing a modified water hyacinth air bag fiber bundle tube: taking a water hyacinth healthy plant with the average diameter of 2.5-4.5 cm at the air sac part, cutting to obtain an air sac and plant stems with the length of 0.8cm above and below the air sac, performing vacuum drying until the moisture content of the plant stems is about 25%, stripping off the surface layer, then peeling off the surface layer, shearing, sieving with a 30-mesh sieve, adding 0.2% by weight of modified shell powder, uniformly mixing to obtain an air sac fiber bundle pipe, taking the air sac fiber bundle pipe, mixing with equal mass of polyaluminum ferric chloride to obtain a solid mixture, performing far infrared heating on the solid mixture to 75 ℃, stirring in the heating process, and simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.16% of the mass of the air sac fiber bundle pipe, and continuing stirring for 10min after spraying is finished to obtain the modified water hyacinth air sac fiber bundle pipe.
Preparing a nano zinc oxide/carbon quantum dot complexing agent: weighing 5kg of barium stearate and 10kg of unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid into a reaction kettle, heating the mixture to 28 ℃, then adding 0.1kg of surfactant, 5kg of deionized water and 0.01kg of defoaming agent, dispersing the mixture for 28min at 75 ℃ and 500rpm, cooling the mixture to room temperature, then adding 10kg of three-dimensional flower-shaped nano zinc oxide powder, 5kg of deionized water and 0.2kg of dispersing agent, heating the mixture in a water bath to 28 ℃, dispersing the mixture for 55min at 220rpm to obtain nano zinc oxide dispersion liquid, adding 5kg of carbon quantum dot solution into the zinc oxide dispersion liquid, stirring and mixing the mixture, placing the mixed liquid into a high-pressure reaction kettle, reacting the mixture for 4.5h at 95 ℃, cooling the mixture to room temperature, washing, centrifuging and drying the product to obtain the nano zinc oxide/carbon quantum dot composite agent.
Preparing a flocculating agent: respectively weighing 25kg of modified water hyacinth air bag fiber bundle tube and 15kg of nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring the mixture for 30min at the speed of 100rpm, uniformly mixing the mixture to obtain a mixture A, then adding 0.4kg of polyaluminum ferric chloride into a ball mill, carrying out ball milling for 3h at the speed of 320rpm, then adding 8kg of sepiolite and 9kg of zeolite, carrying out ball milling for 2h at the speed of 240rpm, finally adding 14kg of active carbon and 0.1kg of adhesive, carrying out ball milling for 1h at the speed of 110rpm to obtain a mixture B, adding the mixture A into the mixture B, then adding 1.5kg of calcium hypochlorite, carrying out ultrasonic oscillation and uniform mixing under the conditions of 30kHz and 120W, placing the mixed material into a drying oven, drying the mixed material for 15min at the constant temperature of 70 ℃ to obtain flocculant powder, and sealing and storing the flocculant powder in a dry and cool place.
The application method of the flocculant powder prepared in the embodiment in sewage treatment is the same as that in the embodiment I.
The three-dimensional flower-like structure of the nano zinc oxide in the first to fourth embodiments is prepared by the method disclosed in the Chinese invention patent with the publication number of "CN 106830052B".
By carrying out on sewageDetecting that the main heavy metal ions in the sewage comprise Pb2+Ions, Cr6+Ion, Cu2+Ions and Cd2+The ion content of the heavy metal in the wastewater of the first to fourth examples was measured before and after the treatment, and the measurement results are shown in the following table:
as can be seen from the above table, the method of the invention can effectively remove heavy metal ions in the industrial heavy metal sewage without generating secondary pollution; meanwhile, the flocculant prepared by the invention can treat Pb in sewage2+Ions, Cr6+Ion, Cu2+Ions, Cd2+The ions have stronger adsorption effect, and are convenient to separate and operate after being used for adsorption treatment in sewage treatment.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (8)
1. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation is characterized by comprising the following steps:
aeration treatment: discharging the sewage into an aeration tank, and spraying O from the bottom of the aeration tank through a nano aeration head3Carrying out aeration treatment on the gas for 3-4 h;
adjusting the pH value: discharging the sewage subjected to aeration treatment into a regulating tank, adding a sodium carbonate/sodium bicarbonate buffer solution into the regulating tank, and regulating the pH value to 6-7;
flocculation: discharging the sewage subjected to pH value adjustment treatment into a sewage treatment tank, adding a flocculating agent into the sewage treatment tank, stirring at the speed of 300rpm for 5min, and standing for 2 h;
air flotation: placing the flocculated sewage into a flotation column for flotation;
precipitation and filtration: placing the sewage subjected to flotation in a sedimentation tank, and standing for sedimentation;
the flocculant comprises the following raw materials in parts by weight: 20-30 parts of modified water hyacinth air bag fiber bundle pipe, 1-2 parts of calcium hypochlorite, 0.1-0.5 part of polyaluminum ferric chloride, 15-20 parts of nano zinc oxide/carbon quantum dot complexing agent, 5-10 parts of sepiolite, 10-15 parts of activated carbon and 5-10 parts of zeolite;
the modified water hyacinth air sac fiber bundle tube is prepared by pretreating healthy water hyacinth plants, adding 0.5-1.0 wt% of modified shell powder, uniformly mixing to obtain an air sac fiber bundle tube, mixing the air sac fiber bundle tube with equal mass of polyaluminum ferric chloride to obtain a solid mixture, carrying out far infrared heating on the solid mixture to 70-75 ℃, stirring in the heating process, simultaneously spraying 1% of chitosan acetic acid solution, wherein the mass of chitosan in the chitosan acetic acid solution is 0.05-0.2% of that of the air sac fiber bundle tube, and continuously stirring for 5-10min after spraying to obtain the modified water hyacinth air sac fiber bundle tube; the 1% chitosan acetic acid solution was: weighing 2g of chitosan, adding 100mL of water, adding 2mL of glacial acetic acid, stirring uniformly, heating to 85 ℃, adding water to a constant volume of 100mL, and keeping the temperature for 45min to obtain a 1% chitosan acetic acid solution.
2. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation of claim 1, wherein the flocculant comprises the following raw materials in parts by weight: 25 parts of modified water hyacinth air bag fiber bundle tube, 1.5 parts of calcium hypochlorite, 0.4 part of polyaluminum ferric chloride, 15 parts of nano zinc oxide/carbon quantum dot complexing agent, 8 parts of sepiolite, 14 parts of activated carbon and 9 parts of zeolite.
3. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation of claim 1, wherein the preparation method of the flocculant is as follows: respectively weighing a modified water hyacinth air bag fiber bundle tube and a nano zinc oxide/carbon quantum dot complexing agent, adding the modified water hyacinth air bag fiber bundle tube and the nano zinc oxide/carbon quantum dot complexing agent into a stirrer, stirring for 30min at the speed of 100rpm, uniformly mixing to obtain a mixture A, adding polyaluminum ferric chloride into a ball mill, ball-milling for 3h at the speed of 300-350 rpm, adding sepiolite and zeolite, ball-milling for 2h at the speed of 200-300 rpm, finally adding activated carbon and an adhesive, ball-milling for 1h at the speed of 100-120 rpm to obtain a mixture B, adding the mixture A into the mixture B, adding calcium hypochlorite, performing ultrasonic oscillation and cooling, uniformly mixing, placing the mixed material into a drying oven, drying at the constant temperature of 65-75 ℃ for 10-15 min to obtain flocculant powder, and sealing and storing in a dry shade.
4. The method for treating industrial heavy metal sewage based on flocculation flotation precipitation as claimed in claim 3, wherein the pretreatment comprises the steps of taking water hyacinth healthy plants with the average diameter of 2.5 cm-4.5 cm at the air sac part, cutting to obtain the air sac and plant stems with the diameters of 0.5-1 cm above and below the air sac, drying in vacuum until the moisture content of the plant stems is 20% -30%, stripping the surface layer, shearing the stripped surface layer, and sieving with a 30-mesh sieve.
5. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation as claimed in claim 4, wherein the modified shell powder is obtained by pickling shell, calcining at 700 ℃, and crushing by a nano crusher.
6. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation of claim 5, wherein the preparation method of the nano zinc oxide/carbon quantum dot complexing agent is as follows: weighing barium stearate and unsaturated fatty acid, placing the barium stearate and the unsaturated fatty acid in a reaction kettle, heating to 25-35 ℃, adding a surfactant, deionized water and a defoaming agent, dispersing at 60-80 ℃ and 500rpm for 20-30 min, cooling to room temperature, adding nano zinc oxide powder, deionized water and a dispersing agent, heating in a water bath to 25-30 ℃, dispersing at 200-300 rpm for 40-60 min to obtain a nano zinc oxide dispersion liquid, adding a carbon quantum dot solution into the zinc oxide dispersion liquid, stirring and mixing, placing the mixed liquid in a high-pressure reaction kettle, reacting at 80-100 ℃ for 3-5 h, cooling to room temperature, washing, centrifuging and drying a product to obtain the nano zinc oxide/carbon quantum dot composite agent.
7. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation of claim 6, wherein the nano zinc oxide is in a three-dimensional flower-shaped structure, and the specific surface area is 1000-1200 square meters per gram.
8. The industrial heavy metal sewage treatment method based on flocculation flotation precipitation of claim 7, wherein the mass ratio of the barium stearate to the unsaturated fatty acid is 1: 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910010691.6A CN109626647B (en) | 2019-01-07 | 2019-01-07 | Industrial heavy metal sewage treatment method based on flocculation flotation precipitation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910010691.6A CN109626647B (en) | 2019-01-07 | 2019-01-07 | Industrial heavy metal sewage treatment method based on flocculation flotation precipitation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109626647A CN109626647A (en) | 2019-04-16 |
| CN109626647B true CN109626647B (en) | 2021-11-19 |
Family
ID=66057923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910010691.6A Active CN109626647B (en) | 2019-01-07 | 2019-01-07 | Industrial heavy metal sewage treatment method based on flocculation flotation precipitation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109626647B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110255690B (en) * | 2019-07-24 | 2022-01-11 | 浙江海洋大学 | Heavy metal wastewater treating agent and application thereof |
| CN113398888B (en) * | 2021-07-13 | 2021-12-31 | 江苏建霖环保科技有限公司 | Composite water purifying agent and preparation method thereof |
| CN115015540B (en) * | 2022-04-17 | 2023-06-16 | 吉林迅准生物技术有限公司 | Preparation method of test strip combining NC (numerical control) film with label and antibody by adopting treatment |
| CN115159775B (en) * | 2022-07-04 | 2023-06-23 | 暨南大学 | Method for removing humus from old garbage leachate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140353257A1 (en) * | 2013-05-29 | 2014-12-04 | Aguas De Manizales S.A. E.S.P. | Compositions for water treatment and methods of using thereof |
| CN105130041A (en) * | 2015-06-26 | 2015-12-09 | 中钢集团马鞍山矿山研究院有限公司 | Improved treatment method of acidic waste water containing heavy metals |
| CN105174567A (en) * | 2015-11-05 | 2015-12-23 | 湖南先科环保有限公司 | Heavy metal wastewater treatment and recovery system and method |
| CN105253979A (en) * | 2015-11-22 | 2016-01-20 | 浙江瀚邦环保科技有限公司 | Flocculation purification agent for heavy metal wastewater in rivers and preparation method and using method thereof |
-
2019
- 2019-01-07 CN CN201910010691.6A patent/CN109626647B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140353257A1 (en) * | 2013-05-29 | 2014-12-04 | Aguas De Manizales S.A. E.S.P. | Compositions for water treatment and methods of using thereof |
| CN105130041A (en) * | 2015-06-26 | 2015-12-09 | 中钢集团马鞍山矿山研究院有限公司 | Improved treatment method of acidic waste water containing heavy metals |
| CN105174567A (en) * | 2015-11-05 | 2015-12-23 | 湖南先科环保有限公司 | Heavy metal wastewater treatment and recovery system and method |
| CN105253979A (en) * | 2015-11-22 | 2016-01-20 | 浙江瀚邦环保科技有限公司 | Flocculation purification agent for heavy metal wastewater in rivers and preparation method and using method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "氧化锌及其复合物纳米材料的合成与催化应用";于行;《中国优秀硕士学位论文全文数据库》;20121015;第4章、第4.2节和图4.1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109626647A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109626647B (en) | Industrial heavy metal sewage treatment method based on flocculation flotation precipitation | |
| US5785862A (en) | Preparation and uses of polyferric sulphate | |
| CN107162093A (en) | A kind of aquaculture water purifying agent and preparation method thereof | |
| WO2014194664A1 (en) | Method for treating wastewater containing cyanides, thiocyanides and heavy metals | |
| CN108514865A (en) | A kind of preparation method of novel magnetic chitosan/sodium alginate plural gel ball | |
| CN102464440B (en) | Method for carrying out decrement on physicochemical and biochemical mixed sludge | |
| CN110372061B (en) | Composite water treatment agent for industrial waste acid treatment and preparation method thereof | |
| CN105948457A (en) | Compounded sludge dewatering conditioner and application method thereof | |
| CN108658300B (en) | Treatment process of ammonia nitrogen wastewater | |
| CN106673299A (en) | Sewage step-by-step dephosphorization and purification process | |
| CN107434315B (en) | A kind of method of leaded zinc wirerope sludge and leaded waste hydrochloric acid integrated treatment | |
| CN106311161A (en) | Efficient treatment method of phosphorus wastewater | |
| CN110759629A (en) | Method for enhancing sludge dewatering performance | |
| CN108928981A (en) | A kind of environment-friendly treating process of industrial wastewater | |
| CN102515385B (en) | Treating technology for removing sodium from high sodium salt wastewater and device thereof | |
| CN108569822B (en) | Water body algae pollution purification treatment method | |
| CN1958462A (en) | Method for preparing potassium ferrate by using waste liquid from acid washing steel | |
| CN110436707A (en) | A kind of gallic acid production wastewater biochemistry pre-treating method | |
| CN110304755A (en) | A kind of wastewater treatment method and its processing system containing electrolytic manganese residues | |
| CN109368850A (en) | A kind of desulfurization wastewater recycling treatment system and application method | |
| CN111039448B (en) | Method for removing manganese impurities in acidic solution by ozone | |
| CN114873810A (en) | Method for vaporizing organic sewage by using irradiation sterilization technology | |
| CN212425805U (en) | Treatment recycling system for electric demisting wastewater and/or electric precipitation wastewater | |
| CN113277653A (en) | Desulfurization wastewater treatment system and method | |
| CN103496778A (en) | Hypophosphorous acid removal agent and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |