CN111302528B - Comprehensive treatment method for copper mine wastewater - Google Patents

Comprehensive treatment method for copper mine wastewater Download PDF

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CN111302528B
CN111302528B CN202010111373.1A CN202010111373A CN111302528B CN 111302528 B CN111302528 B CN 111302528B CN 202010111373 A CN202010111373 A CN 202010111373A CN 111302528 B CN111302528 B CN 111302528B
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wastewater
tank
stage
alkaline
sedimentation tank
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CN111302528A (en
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邓觅
梁培瑜
吴永明
涂文清
游海林
姚忠
刘煜
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Jiangxi Academy Of Sciences
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultra-violet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/542Phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/203Iron or iron compound
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/206Manganese or manganese compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

Abstract

The invention belongs to the technical field of environmental protection, and particularly relates to a comprehensive treatment method for copper ore mine wastewater. Under the condition of not adjusting pH, the method firstly treats the high-COD alkaline wastewater in a centralized way, so that the removal rate of COD reaches more than 80 percent. Then mixing the alkaline treatment water with low COD as a neutralizer with the acidic wastewater to remove high heavy metals in the acidic wastewater, thereby reducing the subsequent treatment cost of sludge and CaSO4The risk of pipe fouling is increased to increase the treatment life of the entire treatment process. The method can effectively remove COD, SS and heavy metals, has the characteristics of high efficiency, strong shock load resistance, no secondary pollution, no need of additional nutrient source in the using process and the like, has low investment and operation cost and simple and convenient operation, and can be suitable for treating the copper mine wastewater.

Description

Comprehensive treatment method for copper mine wastewater
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a comprehensive treatment method for copper ore mine wastewater.
Background
The copper mine wastewater mainly comprises sulfur-containing acidic wastewater in a mining area and overflow alkaline wastewater in a concentrating area; sulfide-containing ores are produced in large quantities by the combined action of oxygen, water and sulfide in the air under the action of biocatalytic oxidation by thiophilus and other leaching bacteria2-、SO4 2-And heavy metal ions, and is more beneficial to the action of thiobacillus and other mineral leaching bacteria and the dissolution of the heavy metal ions under the acidic condition, therebyThe production of acidic wastewater is aggravated. If the acid waste water is not treated, serious environmental pollution is caused, and the acid waste water is treated at higher cost, so that the heavy economic burden is caused to mines.
In copper mine wastewater, the pH of acidic wastewater is 2-3, the COD is low, and the contents of heavy metals such as Cu, Zn, Fe, Mn, Pb and the like are high; the pH value of the alkaline wastewater is 12-13, the COD is high (mainly many inorganic reducing substances and few biochemically degradable organic matters) and the heavy metal content is low; the water amount of the acid wastewater is about 3 times of that of the alkaline wastewater.
In the prior art, the main method for acidic wastewater in mine wastewater is to add lime or alkaline wastewater, discharge or recycle the acidic wastewater after the acidic wastewater reaches the standard, and the acidic wastewater generated by sulfide mine contains a large amount of sulfate ions, and the acidic wastewater is easy to generate calcium sulfate precipitation by directly adding lime, thereby causing calcium accumulation and blockage of pipelines. The alkaline wastewater is also used for directly regulating neutralization, but the simple neutralization does not consider the high COD condition in the alkaline wastewater and has little effect on removing mineral substances and heavy metals in the alkaline wastewater. The treated effluent can not stably reach the standard and can not meet the recycling requirement.
In recent years, a high-concentration slurry treatment process is developed, on the basis of the traditional lime neutralization process, part of bottom slag formed by acid-base neutralization of wastewater is circulated, and is fully mixed with lime serving as a neutralization reagent and then enters an acid-base reaction tank. The purpose of returning is to make full use of the lime which is wrapped in the bottom slag and has no complete reaction so as to reduce the lime consumption; meanwhile, the reflux bottom slag after the circulating flocculation is used as calcium sulfate crystal seeds in the process of mixing with lime, so that a growing place and a carrier are provided for newly generated precipitates such as calcium sulfate, hydroxide and the like, the adsorption probability of the precipitates on pipelines and equipment is reduced, floc particles are further increased, the sedimentation speed of the floc is increased, the concentration and the treatment capacity of the bottom slag are further improved, and the water treatment cost is effectively reduced. And then adding biological agents and oxidizing agents on the basis, and referring to the attached figure 1 of the specification for ensuring the treatment effect. However, the treatment process only considers the neutralization of acid-base wastewater to reduce lime, but does not consider the influence of high COD and high flotation agent on the overall treatment effect, and the treated water showsLow pH, unstable COD, high mineralization and total iron content, and high treatment cost up to 5.6 yuan/m3
Disclosure of Invention
The invention aims to solve the problems and provides a comprehensive treatment method for copper mine wastewater, which fully combines the water quality and water quantity characteristics of acidic wastewater and alkaline wastewater in the copper mine wastewater, so that the treated wastewater can stably reach the standard and can meet the recycling requirement, and the use of medicaments is reduced. The specific technical scheme is as follows:
a copper mine wastewater comprehensive treatment method comprises the following steps: the mine wastewater comprises acidic wastewater and alkaline wastewater; the method comprises the following steps:
(1) the alkaline wastewater directly enters a high-efficiency flocculation inclined plate sedimentation tank, and large-particle slag and metal ions in the wastewater are removed under the action of a flocculating agent and return sludge;
(2) the effluent of the high-efficiency flocculation inclined plate sedimentation tank enters an air floatation tank, and oil, a flotation reagent and fine mineral particle colloid-state suspended matters in the wastewater are removed under the action of micro bubbles;
(3) the effluent of the air floatation tank enters into O3UV reaction tank for efficient oxidation of organic pollutants and S under ozone and UV irradiation2-And the like, so as to realize the high-efficiency removal of COD in the alkaline wastewater;
(4)O3mixing the effluent of the UV reaction tank and the acidic wastewater in proportion and feeding the mixture into a sectional sedimentation tank, wherein the sectional sedimentation tank is set to be four stages, ferrate mixed oxidant is added into a stage I, lime milk is added into a stage II-IV to control pH value so as to realize sectional sedimentation removal of heavy metals in the wastewater;
(5) after being treated by the sectional sedimentation tank, the effluent enters a flocculation sedimentation tank, and a composite flocculant is added to realize standard discharge;
the acid wastewater is sulfur-containing wastewater in a mine mining area; the alkaline wastewater is overflow wastewater of a mine beneficiation area.
Further, cationic PAM is put into the high-efficiency flocculation inclined plate sedimentation tank according to the mass ratio of 0.1-0.2 per mill, partial sludge in the sludge concentration area flows back and circulates to the mixing area, and the sludge flows back and circulates to the mixing areaThe proportion is 15-20%; the diameter of the micro bubble in the air floatation tank is 25-35 mu m, the aeration intensity is 105-115 m3/(m2·h)。
Further, O3The UV reaction tank adopts a low-pressure mercury lamp which can generate 185nm wave band vacuum ultraviolet rays, the power is 35-40W, and the contact reaction time is 50-60 min; the concentration of ozone is 5.5-6.0mg/L, and the contact reaction time is 50-60 min.
Further, the pH range of the stage I of the sectional sedimentation tank is controlled to be 2-4 by adjusting the adding proportion of the acidic wastewater and the alkaline wastewater; controlling the pH range of the II-stage to be 4-6; controlling the pH range of the III grade to be 6-8; and controlling the pH value of the IV grade to be 8-9. The iron/tin removal of the I grade, the copper/aluminum/chromium precipitation of the II grade, the zinc/nickel neutralization treatment of the III grade and the manganese/lead/cadmium precipitation of the IV grade by adding alkali are realized.
Further, the ferrate mixed oxidant comprises the following components in parts by mass: 4 to 5 parts of K2FeO42-3 parts of polyoxyethylene and 1-2 parts of KMnO413-16 parts of hydroxyethylidene diphosphonic acid, 12-14 parts of polyepoxysuccinic acid and 60-65 parts of deionized water; the adding amount is 1.5-2.5% of the mass of the alkaline wastewater; exhibits strong oxidation properties K2FeO4Is an active preparation, and is prepared by taking non-toxic, cheap and excellent-performance non-degradable high-molecular polyoxyethylene, hydroxyethylidene diphosphonic acid, polyepoxysuccinic acid and the like as carriers, thereby solving the problem of weak durability of the traditional oxidant.
Further, the composite flocculant in the step (5) is a compound mixture of polyferric silicate sulfate (PFSS), polyaluminium chloride (PAC) and anionic Polyacrylamide (PAM), and the adding proportion of each component is as follows: 0.5-1.0 mg/L PFSS (in SiO)2Calculated), 20-25 mg/L PAC and 0.1-0.2 mg/L PAM.
In addition, the invention also provides a sectional sedimentation tank for the comprehensive treatment method, which comprises the following steps: the segmented sedimentation tank comprises a first-stage tank, a second-stage tank, a third-stage tank and a fourth-stage tank of a four-stage stepped reactor which are connected in sequence, wherein the four-stage stepped reactor is of an upper cylindrical tank body and a bottom conical structure;
the I-stage tank is provided with an alkaline wastewater inlet pipe and an acidic wastewater inlet pipe, the alkaline wastewater inlet pipe is arranged on the wall of the tank, the acidic wastewater inlet pipe is arranged to be water inlet at the center of the tank body and is divided into three parts after entering the tank body, the three parts are respectively inserted into the middle lower part of the tank body in a claw shape through three water inlet branch pipes to realize water inlet, and the water outlet pipe is arranged on the opposite tank body of the alkaline wastewater inlet pipe and is arranged at the middle position of the tank body above the horizontal position of the pipe orifice of;
II level pond, III level ponds and IV level pond structures are unanimous, are the pond body center and intake, and the inlet tube is deepened the lower part and is realized intaking in the pond body, and the afterbody sets up to the horn type export, the horn type export should be provided with the toper guide plate, and the pond body outlet pipe sets up the pond body middle part position in horn type export mouth of pipe horizontal position top.
Furthermore, the included angle between the water inlet branch pipes of the I-stage pool is 120 degrees, and the water inlet branch pipes are 135 degrees with the wall of the cylindrical pool on the vertical plane.
Furthermore, the bottoms of the I-level pool, the II-level pool, the III-level pool and the IV-level pool are all provided with sludge discharge pipes.
The comprehensive treatment method of the invention comprises the steps of firstly, sequentially passing the alkaline wastewater through' high-efficiency precipitation-ultramicro air flotation-O3A physical and chemical treatment process of/UV reaction tank-composite flocculation. One, realize getting rid of large granule slay and metal ion in the waste water under the alkaline environment of high-efficient flocculation inclined plate sedimentation pond: adding cationic PAM (adding proportion is 1.0-2.0 per mill) suitable for alkaline conditions; external sludge circulation is arranged between the sludge concentration area and the mixing area, so that the concentration of water inlet particles can be greatly increased, the collision and aggregation of the particles are promoted, and the flocculation effect is improved; the sludge reflux can improve the utilization efficiency of coagulant and coagulant aid enriched in the sludge, properly reduce the dosage of the medicament and save the operation cost. And secondly, the removal of the flotation agents such as petroleum, second oil, xanthate and the like can be realized through a micro-bubble air flotation method. Thirdly, the water from the ultramicro air floatation tank is subjected to composite strong oxidation to obtain O3UV reaction cell, further oxidizing S2-And the COD can be efficiently removed by waiting for inorganic reducing substances and residual organic pollutants. Fourthly, mixing the treated alkaline wastewater and the acid wastewater in proportion to adjust the pH value in the I-stage tank to be properAdding ferrate mixed oxidant to remove COD in the acid-base mixed wastewater, and adding lime milk to control the pH values of different stages of the II-IV stage tanks, thereby realizing the staged precipitation removal of heavy metal ions. Finally, through the flocculation and precipitation effects of the composite flocculant, all relevant indexes of the effluent are superior to the limit specified in the emission Standard of pollutants for copper, nickel and cobalt (GB25467-2010), and the effluent is discharged up to the standard or reused in enterprises.
The whole process is represented as follows: firstly removing high COD in alkaline wastewater as much as possible, reducing the addition of subsequent oxidants, then entering a 'sectional sedimentation tank', utilizing different pH values required by different heavy metal sedimentation, showing from I → IV as acidity → alkalinity, reducing the use of medicaments such as lime milk and the like, only adding ferrate mixed oxidant into a stage I tank to remove COD and a small part of heavy metals in the acidic wastewater, and controlling different pH ranges in four reaction tanks by accurately controlling the addition proportion of the acidic wastewater and the alkaline wastewater and adding the lime milk through a PLC (programmable logic controller), thereby realizing the removal of heavy metal ions by stage sedimentation.
The stepped settling tank adopted by the invention is provided with effective control of pH values at different stages, particularly, a claw-shaped water inlet pipe is adopted in the stage I tank, a 135-degree water outlet included angle is formed between the claw-shaped water inlet pipe and the wall of the cylindrical tank body, and a certain vortex is formed in the tank through scouring of oblique angle water inlet to the wall surface, so that automatic turbulent mixing without external power is realized, acidic wastewater, alkaline wastewater and added medicaments in the tank body are fully mixed, and the treatment efficiency is greatly increased.
The invention adopts the principle of quality-divided treatment, under the condition of not adjusting pH, the high-COD alkaline wastewater is treated in a centralized way to ensure that the removal rate of COD reaches more than 80 percent; then the alkaline treated water with low COD is taken as a neutralizer to be mixed with the acidic wastewater to realize the removal of high heavy metals in the acidic wastewater, so as to reduce the dosage of acid neutralizers such as lime milk or carbide slag and the like, and further reduce CaSO brought by the dosage4The generation amount of the sediment substances can be reduced firstly, the subsequent treatment cost of the sludge can be reduced, and the CaSO can be reduced secondly4The risk of pipe fouling to increase the overall processThe process life. In addition, the novel stage type sedimentation tank is designed, and the treatment requirements and effects of the method can be further met. The method can effectively remove COD, SS and heavy metals, has the characteristics of high efficiency, strong shock load resistance, no secondary pollution, no need of additional nutrient source in the using process and the like, has low investment and operation cost and simple and convenient operation, and can be suitable for treating the copper mine wastewater.
Drawings
FIG. 1 is a prior art copper mine wastewater treatment process;
FIG. 2 is a copper mine wastewater treatment process according to the present invention;
FIG. 3 is a schematic view of a sectional sedimentation tank according to the present invention;
FIG. 4 is a schematic view of the structure of a stage I tank of the sectional sedimentation tank of the present invention;
FIG. 5 is a top view of the first stage of the sectional settling tank of the present invention;
FIG. 6 is a schematic structural diagram of a second-stage tank, a third-stage tank and a fourth-stage tank of the sectional sedimentation tank of the present invention;
reference numerals
1-I stage pool body; 2-acid wastewater inlet pipe; 3-an alkaline wastewater inlet pipe; 4-water inlet branch pipe; 5-water outlet pipe; 6-water inlet pipe; water outlet pipes of the 7-II stage pool, the III stage pool and the IV stage pool; 8-horn-shaped outlet; 9-conical baffles.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings
The treatment method comprises the following steps: as shown in fig. 2
(1) The alkaline wastewater directly enters a high-efficiency flocculation inclined plate sedimentation tank, and large-particle slag and metal ions in the wastewater are removed in an alkaline environment; cationic PAM is put into the high-efficiency flocculation inclined plate sedimentation tank according to the mass ratio of 0.1-0.2 per mill, partial sludge in the sludge concentration area flows back and circulates to the mixing area, and the backflow proportion is 15-20%.
(2) The effluent of the high-efficiency flocculation inclined plate sedimentation tank enters an air floatation tank, and oil, a flotation reagent and fine mineral particle colloid-state suspended matters in the wastewater are removed under the action of micro bubbles; the diameter of the micro bubble in the air floatation tank is 25 to 35 μm, and an aeration intensity of 105 to 115m3/(m2·h)。
(3) The effluent of the air floatation tank enters into O3UV reaction tank for efficient oxidation of organic pollutants and S under ozone and UV irradiation2-And the like, so as to realize the high-efficiency removal of COD in the alkaline wastewater; o is3The UV reaction tank adopts a low-pressure mercury lamp which can generate 185nm wave band vacuum ultraviolet rays, the power is 35-40W, and the contact reaction time is 50-60 min; the concentration of ozone is 5.5-6.0mg/L, and the contact reaction time is 50-60 min.
(4)O3Mixing the effluent of the UV reaction tank and the acidic wastewater in proportion and feeding the mixture into a sectional sedimentation tank, wherein the sectional sedimentation tank is set to be four stages, ferrate mixed oxidant is added into a stage I, lime milk is added into a stage II-IV to control pH value so as to realize sectional sedimentation removal of heavy metals in the wastewater; the pH range of the stage I control of the sectional sedimentation tank is 2-4; controlling the pH range of the II-stage to be 4-6; controlling the pH range of the III grade to be 6-8; and controlling the pH value of the IV grade to be 8-9, realizing iron/tin removal of the I grade, copper/aluminum/chromium deposition of the II grade, zinc/nickel neutralization treatment of the III grade, and manganese/lead/cadmium deposition of the IV grade by adding alkali.
The ferrate mixed oxidant comprises the following components in parts by mass: 4 to 5 parts of K2FeO42-3 parts of polyoxyethylene and 1-2 parts of KMnO413-16 parts of hydroxyethylidene diphosphonic acid, 12-14 parts of polyepoxysuccinic acid and 60-65 parts of deionized water; the adding amount is 1.5-2.5% of the mass of the alkaline wastewater.
(5) After being treated by the sectional sedimentation tank, the effluent enters a flocculation sedimentation tank, and a composite flocculant is added to realize standard discharge; the composite flocculant is a compound mixture of polymeric ferric sulfate (PFSS), polyaluminium chloride (PAC) and anionic Polyacrylamide (PAM), and the adding proportion of each component is as follows: 0.5-1.0 mg/L PFSS (calculated as SiO 2), 20-25 mg/L PAC and 0.1-0.2 mg/L PAM.
The acid wastewater is sulfur-containing wastewater in a mine mining area; the alkaline wastewater is overflow wastewater of a mine beneficiation area.
The structure of the sectional sedimentation tank is shown in figures 3-6 and comprises a first-stage tank, a second-stage tank, a third-stage tank and a fourth-stage tank of a four-stage stepped reactor which are connected in sequence, wherein the four-stage stepped reactor is of a structure with an upper cylindrical tank body and a bottom conical tank bottom;
the I-stage tank 1 (as shown in figures 4-5) is provided with an alkaline wastewater inlet pipe 3 and an acidic wastewater inlet pipe 2, the alkaline wastewater inlet pipe is arranged on the wall of the tank, the acidic wastewater inlet pipe is arranged to be inlet water at the center of the tank body, the alkaline wastewater inlet pipe is divided into three parts after entering the tank body, the three parts are respectively inserted into the middle lower part of the tank body in a claw shape through three water inlet branch pipes 4 to realize water inlet, and a water outlet pipe 5 is arranged on the tank body on the corresponding surface of the alkaline wastewater inlet pipe 3 and is arranged at the middle position of the tank; the included angle between the water inlet branch pipes 4 of the I-level pool 1 is 120 degrees, and the water inlet branch pipes 4 are 135 degrees with the wall of the cylindrical pool on the vertical plane.
II level pond, III level ponds and IV level pond structures are unanimous (like fig. 6), are the pond body center and intake, and the lower part realizes intaking in the inlet tube 6 gos deep into the pond body, and the afterbody sets up to horn type export 8, horn type export 8 corresponds and is provided with toper guide plate 9, and the pond body outlet pipe sets up the pond body middle part position in 8 mouth of pipe horizontal position tops in horn type export. And sludge discharge pipes are arranged at the bottoms of the first-stage tank, the second-stage tank, the third-stage tank and the fourth-stage tank.
Example 1
The acid waste water of a certain copper mine comes from a bottom sump of an open mining area, acid waste water discharged from a waste rock yard, raffinate of a dump leaching field and copper recovery liquid, and is mainly formed by oxidizing sulfur in waste sulfide ore into sulfuric acid under a certain condition through a series of chemical reactions and microbial catalysis with the surrounding environment.
And the acid wastewater is conveyed to an industrial water treatment station for treatment through a long-distance glass fiber reinforced plastic pipeline. The water sources are respectively a water sump at the bottom of a mining area, a waste rock yard and an extraction workshop, and the annual treatment water amount is about 1450 ten thousand meters3. The water quality condition is as follows:
the alkaline wastewater of the copper mine mainly comprises beneficiation and flotation wastewater of a concentrating mill, and the alkaline water collected in front of a current alkaline wastewater pump room mainly comprises the following three streams of water:
the heavy metal condition in the alkaline waste water is as follows:
the treatment mode shown in figure 1 is adopted before, which has the following problems that the water quality is unstable and the fluctuation is large; the lime milk and the carbide slag are large in usage amount and high in cost, and pipelines are seriously scaled; the reaction tanks are too few, so that the hydraulic retention time is short, the water quality treatment is incomplete and the like.
In order to solve the problems, the wastewater is treated by adopting the treatment method of the invention:
the monitoring of the engineering for 10 months shows that the high-efficiency precipitation-ultramicro air flotation-O3After the/UV reaction tank-composite flocculation' complete treatment system, the quality of effluent water is stable for a long time, the concentrations of target pollutants such as COD, SS, Pb, Cu and Zn in the effluent water respectively reach 45-52 mg/L, 55-63 mg/L, 0.1-0.2 mg/L, 0.2-0.3 mg/L and 0.7-0.9 mg/L, the quality of the effluent water is superior to the limit values specified in the emission standards of pollutants for copper, nickel and cobalt (GB25467-2010), the phenomena of the mineralization degree of the effluent water and the total iron content existing before are well solved, the effluent water is discharged up to the standard or reused in enterprises, and the degree of pipeline scaling is greatly reduced. The water quality of the inlet and outlet water is shown in the following table.
Although the preferred embodiments of the present patent have been described in detail, the present patent is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present patent within the knowledge of those skilled in the art.

Claims (8)

1. A copper mine wastewater comprehensive treatment method is characterized by comprising the following steps: the mine wastewater comprises acidic wastewater and alkaline wastewater; the acidic wastewater is sulfur-containing wastewater in a mine mining area, the alkaline wastewater is overflow wastewater in the mine mining area, and the pH value is more than 12; the method comprises the following steps:
(1) the alkaline wastewater directly enters a high-efficiency flocculation inclined plate sedimentation tank, and large-particle slag and metal ions in the wastewater are removed under the action of a flocculating agent and return sludge;
(2) the effluent of the high-efficiency flocculation inclined plate sedimentation tank enters an air floatation tank, and oil, a flotation reagent and fine mineral particle colloid-state suspended matters in the wastewater are removed under the action of micro bubbles;
(3) the effluent of the air floatation tank enters into O3UV reaction tank for efficiently oxidizing organic pollutants and S in wastewater under ozone and ultraviolet irradiation conditions2-Inorganic reducing substances are used for realizing the high-efficiency removal of COD in the alkaline wastewater;
(4)O3mixing the effluent of the UV reaction tank and the acidic wastewater in proportion and feeding the mixture into a sectional sedimentation tank, wherein the sectional sedimentation tank is set to be four stages, ferrate mixed oxidant is added into a stage I, lime milk is added into a stage II-IV to control pH value so as to realize sectional sedimentation removal of heavy metals in the wastewater; the stage I of the sectional sedimentation tank controls the pH range to be 2-4 by adjusting the adding proportion of the acidic wastewater and the alkaline wastewater; controlling the pH range of the II-stage to be 4-6; controlling the pH range of the III grade to be 6-8; controlling the pH value of the IV grade to be 8-9;
(5) and after the effluent is treated by the sectional sedimentation tank, the effluent enters a flocculation sedimentation tank, and a composite flocculant is added to realize standard discharge.
2. The comprehensive treatment method of the copper mine wastewater according to claim 1, characterized by comprising the following steps: cationic PAM is put into the high-efficiency flocculation inclined plate sedimentation tank according to the mass ratio of 0.1-0.2 per mill, partial sludge in the sludge concentration area reflows and circulates to the mixing area, and the reflowing proportion is 15-20%; the diameter of the micro bubble in the air floatation tank is 25-35 mu m, and the aeration intensity is 105-115 m3/(m2·h)。
3. The comprehensive treatment method of the copper mine wastewater according to claim 1, characterized by comprising the following steps: o is3The UV reaction tank adopts a low-pressure mercury lamp which can generate 185nm wave band vacuum ultraviolet rays, the power is 35-40W, and the contact reaction time is 50-60 min; the concentration of ozone is 5.5-6.0mg/L, and the contact reaction time is 50-60 min.
4. The comprehensive treatment method of the copper mine wastewater according to claim 1, characterized by comprising the following steps: the ferrate mixed oxidant comprises 4-5 parts of K by mass2FeO42-3 parts of polyoxyethylene and 1-2 parts of KMnO413-16 parts of hydroxyethylidene diphosphonic acid, 12-14 parts of polyepoxysuccinic acid and 60-65 parts of deionized water; the adding amount is 1.5-2.5% of the mass of the alkaline wastewater.
5. The comprehensive treatment method of the copper mine wastewater according to claim 1, characterized by comprising the following steps: the composite flocculant in the step (5) is a compound mixture of polyferric silicate sulfate (PFSS), polyaluminium chloride (PAC) and anionic Polyacrylamide (PAM), and the adding proportion of each component is as follows: with SiO2The amount of PFSS is 0.5-1.0 mg/L, PAC is 20-25 mg/L and PAM is 0.1-0.2 mg/L.
6. A staged sedimentation tank for use in the integrated process of claim 1, wherein: the segmented sedimentation tank comprises a first-stage tank, a second-stage tank, a third-stage tank and a fourth-stage tank of a four-stage stepped reactor which are connected in sequence, wherein the four-stage stepped reactor is of an upper cylindrical tank body and a bottom conical structure;
the I-stage tank (1) is provided with an alkaline wastewater inlet pipe (3) and an acidic wastewater inlet pipe (2), the alkaline wastewater inlet pipe is arranged on the wall of the tank, the acidic wastewater inlet pipe is arranged to be fed into the center of the tank body and is divided into three parts after entering the tank body, the three parts are respectively inserted into the middle lower part of the tank body in a claw shape through three water inlet branch pipes (4) to realize water inlet, and a water outlet pipe (5) is arranged on the opposite tank body of the alkaline wastewater inlet pipe (3) and is arranged at the middle position of the tank body above the horizontal position of a pipe orifice of each water inlet branch;
II grades of ponds, III grades of ponds and IV grades of ponds structures are unanimous, are the pond body center and intake, and lower part realization was intake in the inlet tube (6) gos deep into the pond body, and the afterbody sets up to horn type export (8), horn type export (8) correspond and are provided with toper guide plate (9), and the pond body outlet pipe sets up the pond body middle part position in horn type export (8) mouth of pipe horizontal position top.
7. The staged sedimentation tank of claim 6, wherein: the included angle between the water inlet branch pipes (4) of the I-level pool (1) is 120 degrees, and the water inlet branch pipes (4) are 135 degrees with the wall of the cylindrical pool on the vertical plane.
8. The staged sedimentation tank of claim 7, wherein: and sludge discharge pipes are arranged at the bottoms of the first-stage tank, the second-stage tank, the third-stage tank and the fourth-stage tank.
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