CN112299668B - high-COD lead-zinc industrial beneficiation wastewater treatment system and method - Google Patents
high-COD lead-zinc industrial beneficiation wastewater treatment system and method Download PDFInfo
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Abstract
The invention provides a high-COD lead-zinc industrial beneficiation wastewater treatment system, and belongs to the technical field of wastewater treatment. The treatment system comprises a collecting tank, a pretreatment tank, a primary sedimentation tank, a magnetic separation reactor, a catalytic oxidation reaction tank, an MBR tank and a sludge dewatering device which are communicated with a primary sedimentation tank sludge outlet and an MBR tank sludge outlet in sequence. In the invention, high COD lead and zinc industrial beneficiation wastewater is collected by a collecting tank and then enters a pretreatment tank to be mixed with soluble sulfides, and formed sulfide precipitates are removed in a sedimentation tank; the obtained supernatant fluid enters a magnetic separation reactor to deeply remove heavy metal pollutants, water produced by the magnetic separation reaction enters a catalytic oxidation reaction tank, catalytic oxidation reaction is carried out at the front end of the reaction tank to remove residual organic reagents, residual iron ions in water at the tail end of the reaction tank are flocculated, catalytic oxidation reaction liquid containing flocculated sludge enters an MBR tank to carry out membrane separation treatment, and finally water produced by the magnetic separation reaction can meet emission standards.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a high-COD lead-zinc industrial beneficiation wastewater treatment system and method.
Background
The main pollutants in the lead-zinc industrial beneficiation wastewater are residual organic agents and heavy metal pollutants such as copper, zinc, cadmium, lead and the like. COD of the lead-zinc industrial beneficiation wastewater is up to 200-1000 mg/L, which is mainly caused by organic reagent residues in the flotation process, wherein the organic reagent is mainly butyl xanthate and nigrosine, the butyl xanthate has good natural degradation capability, and the nigrosine can be naturally degraded in a longer time compared with the xanthate due to stable structure. At present, part of mining industry is not planned to construct a tailing pond, and mineral separation produced water directly enters a sewage treatment system without long-term natural degradation and precipitation of the tailing pond, so that the content of flotation agents and heavy metals in the wastewater is high.
At present, the treatment process of the beneficiation wastewater in the high-COD lead-zinc industry mainly comprises electrocatalytic oxidation, ozone catalytic oxidation, ion exchange and other advanced oxidation processes, and the processes have good treatment effects on residual organic agents, but have poor treatment capability on heavy metal pollutants. The multistage coupling oxidation processes such as ozone, ultraviolet light catalytic oxidation, ion exchange, electrochemistry, biochemical treatment, two-stage RO membrane and the like have good treatment effects on organic matters and heavy metals, but the problems of high operation cost, complex process, high field operation difficulty and the like generally exist, and particularly the concentrated solution cannot be treated by using NF and RO membrane technology.
Disclosure of Invention
In view of the above, the invention aims to provide a system and a method for treating high-COD lead-zinc industrial beneficiation wastewater. The treatment system and the treatment method provided by the invention can effectively remove the residual organic medicament and heavy metal pollutants in the wastewater, and have low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high COD lead and zinc industrial beneficiation wastewater treatment system, which comprises a collecting tank;
the inlet of the pretreatment tank is communicated with the outlet of the collection tank, and the pretreatment tank is also communicated with a first dosing device which is used for adding soluble sulfides into the pretreatment tank;
the inlet of the primary sedimentation tank is communicated with the outlet of the pretreatment tank, and the primary sedimentation tank is provided with a first clear liquid outlet and a first sludge outlet;
the inlet is communicated with the first clear liquid outlet, and Fe is arranged in the magnetic separation reactor 3 O 4 A base filler;
the inlet is communicated with the outlet of the magnetic separation reactor, a second dosing device and a third dosing device are arranged at the front end of the catalytic oxidation reaction tank, a fourth dosing device and a fifth dosing device are sequentially arranged at the tail end of the catalytic oxidation reaction tank, the second dosing device is used for adding an oxidant into the catalytic oxidation reaction tank, and the third dosing device is used for adding Fe into the catalytic oxidation reaction tank 2+ The fourth dosing device is used for adding an alkali reagent into the catalytic oxidation reaction tank, and the fifth dosing device is used for adding a coagulant aid into the catalytic oxidation reaction tank;
an inlet of the MBR tank is communicated with an outlet of the catalytic oxidation reaction tank, and a hollow fiber membrane is arranged in the MBR tank; the MBR tank is also provided with a second clear liquid outlet and a second sludge outlet;
and the inlet is communicated with the first sludge outlet and the second sludge outlet, and the sludge dewatering device is provided with a third sludge outlet.
Preferably, the soluble sulfide is Na 2 S、K 2 S and Li 2 One of S;
the Fe is 3 O 4 The base filler isTiO 2 -Fe 3 O 4 Composite material, siO 2 -Fe 3 O 4 Composite material and graphene-Fe 3 O 4 One of the composite materials.
Preferably, the oxidant is one of hydrogen peroxide, potassium persulfate and sodium persulfate, and the mass fraction of the hydrogen peroxide is 25% -30%;
the Fe is 2+ The base catalyst is soluble ferrous salt;
the alkali reagent is CaO, naOH and Ca (OH) 2 One or more of the following;
the coagulant aid is polyacrylamide.
Preferably, the hollow fiber membrane is made of PTFE or PVDF, and has a membrane pore size of 0.1-0.5 μm.
The invention provides a method for treating high COD lead and zinc industrial beneficiation wastewater based on the treatment system, which comprises the following steps:
(1) The high COD lead and zinc industrial beneficiation wastewater enters a collecting tank for collection;
(2) Inputting the beneficiation wastewater in the collecting tank into a pretreatment tank, and stirring, mixing and pretreating the beneficiation wastewater and soluble sulfides added by the first dosing device to obtain pretreated water;
(3) The pretreated water enters a primary sedimentation tank for standing and sedimentation to obtain supernatant and first sludge, and the first sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge;
(4) The supernatant enters a magnetic separation reactor for heavy metal adsorption separation to obtain water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reaction enters the front end of the catalytic oxidation reaction tank and is added with the oxidant added by the second chemical adding device and the Fe added by the third chemical adding device 2+ Mixing the base catalysts, and carrying out catalytic oxidation reaction to obtain catalytic oxidation reaction liquid;
the catalytic oxidation reaction liquid flows to the tail end of the catalytic oxidation reaction tank and is mixed with an alkaline reagent added by a fourth dosing device to obtain a catalytic oxidation reaction liquid with the pH value of 7-8;
mixing the catalytic oxidation reaction liquid with the pH value of 7-8 with a coagulant aid added by a fifth dosing device, and performing flocculation reaction to obtain a catalytic oxidation reaction liquid containing flocculated sludge;
(6) And the catalytic oxidation reaction liquid containing the flocculated sludge enters an MBR tank for membrane separation treatment to obtain second sludge and final effluent, and the second sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge.
Preferably, the COD content in the high COD lead-zinc industrial beneficiation wastewater is 200-1000 mg/L.
Preferably, the effluent flow of the beneficiation wastewater collection liquid is 4000-6000 m 3 /d。
Preferably, the addition amount of the soluble sulfides is 50-150 mg/L; the retention time of the beneficiation wastewater in the pretreatment tank is 10-30 min;
the standing and precipitating time is 30-60 min.
Preferably, the residence time of the supernatant in the magnetic separation reactor is 30-60 min.
Preferably, the addition amount of the oxidant is 100-200 mg/L; the Fe is 2+ The adding amount of the base catalyst is 400-600 mg/L; the addition amount of the coagulant aid is 50-100 mg/L; the residence time of the water produced by the magnetic separation reaction in the catalytic oxidation reaction tank is 20-120 min.
The invention provides a high COD lead-zinc industrial beneficiation wastewater treatment system which comprises a collecting tank, a pretreatment tank, a primary sedimentation tank, a magnetic separation reactor, a catalytic oxidation reaction tank, an MBR tank and a sludge dewatering device communicated with a primary sedimentation tank sludge outlet and an MBR tank sludge outlet. In the invention, the high COD lead-zinc industrial beneficiation wastewater enters a collecting tank for collection, then enters a pretreatment tank for mixing with soluble sulfides, and S is formed in the mixing process 2- Carrying out displacement reaction with heavy metal pollutants such as copper, zinc, cadmium, lead and the like in the wastewater to convert the copper, zinc, cadmium, lead and the like into slightly soluble sulfide precipitates, and removing the slightly soluble sulfide precipitates in a sedimentation tank in a standing sedimentation manner; allowing the supernatant after standing and precipitation to enter a magnetic separation reactor, and utilizing the adsorption capacity of magnetic filler in the reactor to obtain a supernatantDeep removing residual heavy metal pollutants, wherein the obtained magnetic separation reaction product water carries a part of Fe 2+ And Fe (Fe) 3+ Wherein Fe is 2+ Can be used as Fe 2+ The base catalyst directly participates in catalytic oxidation reaction, and can reduce the content of Fe 2+ The addition amount of the catalyst is favorable for reducing the cost; the water produced by the magnetic separation reaction enters the front end of the catalytic oxidation reaction tank, and the organic medicament in the water produced by the magnetic separation reaction is Fe 2+ Catalytic oxidation reaction is carried out with an oxidant under the catalysis of a base catalyst, so that the COD (chemical oxygen demand) amount in the wastewater is reduced to the standard content; after the catalytic oxidation reaction, the obtained catalytic oxidation reaction liquid contains Fe 2+ And Fe (Fe) 3+ After flowing to the tail end of the catalytic oxidation reaction tank, the mixture is mixed with an alkali reagent, the pH value is increased to 7-8, and Fe at the moment 2+ 、Fe 3+ Is converted into Fe (OH) n Precipitation, forming Fe (OH) under flocculation of coagulant aid n The flocculated sludge is dispersed in the catalytic oxidation reaction liquid; introducing the catalytic oxidation reaction liquid containing flocculated sludge into an MBR tank, and adding Fe (OH) n The flocculated sludge can form coprecipitation with the sludge on the surface of the hollow fiber membrane, has a purifying effect on the hollow fiber membrane, and can effectively relieve the problem of membrane fouling, thereby reducing the cost of replacing the filtering membrane. After being filtered by the hollow fiber membrane, the generated final effluent can reach the class III emission standard in the surface water environment quality standard, and the sludge generated by the primary sedimentation tank and the MBR tank enters a sludge dewatering device for dewatering treatment, so that the obtained dewatered sludge is transported to the outside.
Meanwhile, the treatment method provided by the invention has the advantages of short flow, simple operation, high process relativity, strong impact load resistance and the like, only needs to adjust the pH value once in the treatment process, solves the problems of complex process, high cost, high operation difficulty and the like in the treatment of the high COD lead-zinc industrial beneficiation wastewater by the advanced oxidation method, and has great reference value for upgrading and reforming the high COD beneficiation wastewater treatment when the COD is in the range of 200-1000 mg/L along with the difference of COD of different wastewater, compared with the existing advanced oxidation method, the operation cost of the method is only 1-6 yuan/ton water, and the operation cost is reduced by at least 40%.
Drawings
FIG. 1 is a schematic diagram of a high COD lead and zinc industrial beneficiation wastewater treatment system of the present invention.
Detailed Description
The invention provides a high COD lead and zinc industrial beneficiation wastewater treatment system, which comprises a collecting tank;
the inlet of the pretreatment tank is communicated with the outlet of the collection tank, and the pretreatment tank is also communicated with a first dosing device which is used for adding soluble sulfides into the pretreatment tank;
the inlet of the primary sedimentation tank is communicated with the outlet of the pretreatment tank, and the primary sedimentation tank is provided with a first clear liquid outlet and a first sludge outlet;
the inlet is communicated with the first clear liquid outlet, and Fe is arranged in the magnetic separation reactor 3 O 4 A base filler;
the inlet is communicated with the outlet of the magnetic separation reactor, a second dosing device and a third dosing device are arranged at the front end of the catalytic oxidation reaction tank, a fourth dosing device and a fifth dosing device are sequentially arranged at the tail end of the catalytic oxidation reaction tank, the second dosing device is used for adding an oxidant into the catalytic oxidation reaction tank, and the third dosing device is used for adding Fe into the catalytic oxidation reaction tank 2+ The fourth dosing device is used for adding an alkali reagent into the catalytic oxidation reaction tank, and the fifth dosing device is used for adding a coagulant aid into the catalytic oxidation reaction tank;
an inlet of the MBR tank is communicated with an outlet of the catalytic oxidation reaction tank, and a hollow fiber membrane is arranged in the MBR tank; the MBR tank is also provided with a second clear liquid outlet and a second sludge outlet;
and the inlet is communicated with the first sludge outlet and the second sludge outlet, and the sludge dewatering device is provided with a third sludge outlet.
The invention provides a high COD lead-zinc industrial beneficiation wastewater treatment system which comprises a collecting tank. The invention has no special requirements on the type and specification of the collecting tank, and the collecting tank well known by the person skilled in the art can be used for collecting.
The invention provides high CODThe lead-zinc industrial beneficiation wastewater treatment system comprises a pretreatment tank, wherein an inlet of the pretreatment tank is communicated with an outlet of the collection tank, a first dosing device is further communicated with the pretreatment tank, and the first dosing device is used for adding soluble sulfides into the pretreatment tank. The invention has no special requirements on the types and specifications of the pretreatment tanks, and the pretreatment tanks well known to those skilled in the art can be used for completing the mixing process. The present invention has no special requirements for the first dosing device, and can control the dosing amount of the drug by using dosing devices well known to those skilled in the art. In the present invention, the soluble sulfide is preferably Na 2 S、K 2 S and Li 2 One of S.
The high COD lead and zinc industrial beneficiation wastewater treatment system provided by the invention comprises a primary sedimentation tank, wherein an inlet of the primary sedimentation tank is communicated with an outlet of the pretreatment tank, and the primary sedimentation tank is provided with a first clear liquid outlet and a first sludge outlet. The invention has no special requirements on the types and specifications of the primary sedimentation tank, and the primary sedimentation tank well known by the person skilled in the art is used for realizing the sedimentation of the wastewater. The invention has no special requirements on the setting positions of the first clear liquid outlet and the first sludge outlet, and the invention can be correspondingly designed according to the actual working conditions.
The invention provides a high COD lead and zinc industrial beneficiation wastewater treatment system which comprises a magnetic separation reactor, wherein an inlet of the magnetic separation reactor is communicated with a first clear liquid outlet, and Fe is arranged in the magnetic separation reactor 3 O 4 And (3) a base filler. The present invention is not particularly limited in the kind of the magnetic separation reactor, and a magnetic separation reactor well known to those skilled in the art may be used. In the present invention, the Fe 3 O 4 The base filler is preferably TiO 2 -Fe 3 O 4 Composite material, siO 2 -Fe 3 O 4 Composite material and graphene-Fe 3 O 4 One of the composite materials; the Fe is 3 O 4 In the base filler, fe 3 O 4 The mass percentage of (2) is preferably 50 to 70%, more preferably 60%.
The high COD lead and zinc industrial beneficiation wastewater treatment system provided by the invention comprises a catalytic oxidation reaction tank, wherein an inlet of the catalytic oxidation reaction tank is communicated with an outlet of the magnetic separation reactor. In the invention, the catalytic oxidation reaction tank is preferably rectangular in shape and comprises a front end and a tail end, wherein the front end of the catalytic oxidation reaction tank is provided with a second dosing device and a third dosing device, and the tail end of the catalytic oxidation reaction tank is sequentially provided with a fourth dosing device and a fifth dosing device. The second dosing device, the third dosing device, the fourth dosing device and the fifth dosing device are not particularly required, and dosing devices which are well known to those skilled in the art can be used for controlling the dosing amount of the medicaments.
In the invention, the second dosing device is used for adding an oxidant into the catalytic oxidation reaction tank, wherein the oxidant is preferably one of hydrogen peroxide, potassium persulfate and sodium persulfate, and the mass fraction of the hydrogen peroxide is preferably 25-30%.
The third dosing device is used for adding Fe into the catalytic oxidation reaction tank 2+ A base catalyst of Fe 2+ The base catalyst is preferably a soluble ferrous salt, more preferably FeSO 4 、FeCl 2 、FeNO 3 One of them.
The fourth dosing device is used for adding alkaline reagents into the catalytic oxidation reaction tank, wherein the alkaline reagents are preferably CaO, naOH and Ca (OH) 2 One or more of them.
The fifth medicine adding device is used for adding coagulant aid into the catalytic oxidation reaction tank, the coagulant aid is preferably polyacrylamide, and the molecular weight of the polyacrylamide is preferably 8000-10000.
The high-COD lead-zinc industrial beneficiation wastewater treatment system provided by the invention comprises an MBR (membrane bioreactor) tank, wherein an inlet of the MBR tank is communicated with an outlet of the catalytic oxidation reaction tank, and a hollow fiber membrane is arranged in the MBR tank. The invention has no special requirements on the type and specification of the MBR tank, and the MBR tank well known to the person skilled in the art can be used. In the present invention, the hollow fiber membrane is preferably made of PTFE or PVDF, and the pore diameter of the membrane is preferably 0.1 to 0.5. Mu.m, more preferably 0.1. Mu.m.
In the present invention, the MBR tank includes a second clear liquid outlet and a second sludge outlet. The invention has no special requirements on the positions of the second clear liquid outlet and the second sludge outlet, and the invention is designed correspondingly according to the actual situation.
The high-COD lead-zinc industrial beneficiation wastewater treatment system provided by the invention comprises a sludge dewatering device, wherein an inlet of the sludge dewatering device is communicated with the first sludge outlet and the second sludge outlet, and the sludge dewatering device is provided with a third sludge outlet. The present invention has no special requirement for the sludge dewatering device, and the sludge dewatering device well known to the person skilled in the art can be used.
The schematic diagram of the high COD lead-zinc industrial beneficiation wastewater treatment system is shown in figure 1.
The invention provides a method for treating high COD lead-zinc industrial beneficiation wastewater based on the treatment system, which comprises the following steps:
(1) The high COD lead and zinc industrial beneficiation wastewater enters a collecting tank for collection;
(2) Inputting the beneficiation wastewater in the collecting tank into a pretreatment tank, and stirring, mixing and pretreating the beneficiation wastewater and soluble sulfides added by the first dosing device to obtain pretreated water;
(3) The pretreated water enters a primary sedimentation tank for standing and sedimentation to obtain supernatant and first sludge, and the first sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge;
(4) The supernatant enters a magnetic separation reactor for heavy metal adsorption separation to obtain water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reaction enters the front end of the catalytic oxidation reaction tank and is added with the oxidant added by the second chemical adding device and the Fe added by the third chemical adding device 2+ Mixing the base catalysts, and carrying out catalytic oxidation reaction to obtain catalytic oxidation reaction liquid;
the catalytic oxidation reaction liquid flows to the tail end of the catalytic oxidation reaction tank and is mixed with an alkaline reagent added by a fourth dosing device to obtain a catalytic oxidation reaction liquid with the pH value of 7-8;
mixing the catalytic oxidation reaction liquid with the pH value of 7-8 with a coagulant aid added by a fifth dosing device, and performing flocculation reaction to obtain a catalytic oxidation reaction liquid containing flocculated sludge;
(6) And the catalytic oxidation reaction liquid containing the flocculated sludge enters an MBR tank for membrane separation treatment to obtain second sludge and final effluent, and the second sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge.
In the invention, the high COD lead-zinc industrial beneficiation wastewater firstly enters a collecting tank for collection. The high COD lead-zinc industrial beneficiation wastewater contains residual organic chemicals and heavy metal pollutants. In the present invention, the residual organic agent is preferably butyl xanthate, nigrosine and a rechecking higher alcohol; the heavy metals include copper, zinc, cadmium and lead. In the invention, the COD content in the high COD lead and zinc industrial beneficiation wastewater is preferably 200-1000 mg/L. The invention has no special requirement on the content of the heavy metal pollutants, and the high COD lead zinc industrial beneficiation wastewater containing any heavy metal pollutants can be treated by using the device and the method provided by the invention.
The invention inputs the beneficiation wastewater in the collecting tank into the pretreatment tank, and carries out stirring and mixing pretreatment with the soluble sulfide added by the first dosing device to obtain pretreated water. In the invention, the effluent flow of the beneficiation wastewater collection liquid is preferably 4000-6000 m 3 /d; the addition amount of the soluble sulfides is preferably 50-150 mg/L, more preferably 80-120 mg/L; the retention time of the beneficiation wastewater collection liquid in the pretreatment tank is preferably 10-30 min, and more preferably 20min. The invention can make S by stirring and mixing 2- And the wastewater undergoes displacement reaction with heavy metal pollutants such as copper, zinc, cadmium, lead and the like in the wastewater, so that the copper, zinc, cadmium and lead are converted into slightly soluble sulfide precipitates which are dispersed in the pretreated water.
And (3) enabling the pretreated water to enter a primary sedimentation tank for standing and sedimentation to obtain supernatant and first sludge. In the present invention, the time for the standing precipitation is preferably 30 to 60 minutes, more preferably 40 to 50 minutes. And the first sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge. The specific operation mode of the dehydration treatment is not particularly required, and a sludge dehydration mode well known to a person skilled in the art can be used. After the dewatered sludge is obtained, the dewatered sludge is preferably treated for its outward transportation.
And (3) allowing the supernatant fluid to enter a magnetic separation reactor for heavy metal adsorption separation to obtain water produced by the magnetic separation reactor. In the present invention, the residence time of the supernatant in the magnetic separation reactor is preferably 30 to 60 minutes, more preferably 40 to 50 minutes. The invention can deeply remove the residual heavy metal pollutants in the supernatant by utilizing the adsorption capacity of the magnetic filler in the reactor.
The water produced by the magnetic separation reaction enters the front end of the catalytic oxidation reaction tank and is added with the oxidant added by the second chemical adding device and the Fe added by the third chemical adding device 2+ Mixing the base catalysts, and carrying out catalytic oxidation reaction to obtain catalytic oxidation reaction liquid. In the present invention, the amount of the oxidizing agent to be added is preferably 100 to 200mg/L, more preferably 60 to 120mg/L; the Fe is 2+ The amount of the base catalyst to be added is preferably 0.4 to 0.6g/L, more preferably 0.45 to 0.55g/L. In the present invention, the supernatant liquid carries part of Fe when passing through the magnetic separation reactor 2+ And Fe (Fe) 3+ Wherein Fe is 2+ Can be used as Fe 2+ The base catalyst directly participates in catalytic oxidation reaction, and can contain Fe 2+ The addition amount of the catalyst is reduced by about 20 percent, which is beneficial to reducing the cost.
The catalytic oxidation reaction liquid flows to the tail end of the catalytic oxidation reaction tank and is mixed with an alkaline reagent added by a fourth dosing device to obtain a catalytic oxidation reaction liquid with the pH value of 7-8; and mixing the catalytic oxidation reaction liquid with the pH value of 7-8 with a coagulant aid added by a fifth dosing device, and performing flocculation reaction to obtain the catalytic oxidation reaction liquid containing flocculated sludge. In the present invention, the addition amount of the coagulant aid is preferably 50 to 100mg/L, more preferably 60 to 80mg/L. In the present invention, the residence time of the supernatant in the magnetic separation reactor is preferably 30 to 60 minutes, more preferably 40 to 50 minutes.
In the invention, the organic medicament in the wastewater is prepared by the method that Fe 2+ Catalytic oxidation reaction is carried out with an oxidant under the catalysis of a base catalyst, so that the COD (chemical oxygen demand) amount in the wastewater is reduced to the standard content; after the catalytic oxidation reaction, the obtained catalytic oxidation reaction liquid contains Fe 2+ And Fe (Fe) 3+ To catalytic oxidationAfter the tail end of the reaction tank, firstly mixing with alkali reagent, raising pH value to 7-8, at this time Fe 2+ 、Fe 3+ Is converted into Fe (OH) n Precipitation, forming Fe (OH) under flocculation of coagulant aid n The flocculated sludge is dispersed in the catalytic oxidation reaction liquid.
And the catalytic oxidation reaction liquid containing the flocculated sludge enters an MBR tank for membrane separation treatment to obtain second sludge and final effluent, and the second sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge. The membrane separation treatment is preferably carried out under aeration conditions, and the aeration amount is preferably 30 to 60L/min. In the invention, the catalytic oxidation reaction liquid containing the flocculated sludge enters the MBR tank, and the Fe (OH) n flocculated sludge can form coprecipitation with the sludge on the surface of the hollow fiber filtering membrane, so that the hollow fiber filtering membrane has a purifying effect, and the problem of membrane fouling can be effectively relieved, thereby reducing the cost for replacing the filtering membrane.
The specific operation mode of the dehydration treatment is not particularly required, and a sludge dehydration mode well known to a person skilled in the art can be used. After the dewatered sludge is obtained, the dewatered sludge is preferably treated for its outward transportation. After the final water is obtained, the invention can be directly discharged or recycled.
The system and the method for treating the high COD lead and zinc industrial beneficiation wastewater provided by the invention are described in detail below by combining examples, but the system and the method are not to be construed as limiting the protection scope of the invention.
Example 1
The treatment system of the invention is used for treating the wastewater of a lead-zinc concentrating plant, and the quality of the concentrating wastewater is shown in table 1:
TABLE 1 quality of wastewater from certain lead-zinc concentrating mills (unit: mg/L, pH value dimensionless)
| Index of water quality | COD | pH value of | Cu | Zn | Cd | As | Pb |
| Content of | 236.8 | 5.41 | 11.84 | 31.63 | 8.10 | 20.45 | 35.28 |
The processing method comprises the following steps:
(1) The beneficiation wastewater is led into a collecting tank for collection;
(2) Collecting liquid of mineral separation wastewater of 250m 3 The flow of/h is led into a pretreatment tank, and 100mg/L Na is added into the pretreatment tank through a first chemical adding device 2 S, stirring and mixing for 30min to obtain pretreated water;
(3) Introducing the pretreated water into a primary sedimentation Chi Jingzhi for sedimentation for 30min to obtain supernatant and first sludge, and allowing the first sludge to enter a sludge dewatering device for dewatering treatment to obtain dewatered sludge for outward transportation treatment;
(4) The supernatant liquid enters into the filler to be TiO 2 -Fe 3 O 4 The magnetic separation reactor of the composite material stays for 40min to obtain the water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reactor is introduced into the catalytic oxidation reaction tank, and H is respectively added to the front end of the catalytic oxidation reaction tank through the second chemical adding device and the third chemical adding device 2 O 2 50mg/L and FeSO 4 400mg/L, and carrying out catalytic oxidation reaction;
(6) The catalytic oxidation reaction liquid obtained in the step (5) flows to the tail end of the catalytic oxidation reaction tank, firstly NaOH is added into a reaction zone through a fourth dosing device, the pH value of the reaction liquid is regulated to 7-8, and then 50mg/L of PAM is added into the reaction zone through a fifth dosing device, so that the catalytic oxidation reaction liquid containing flocculated sludge is obtained;
(7) Introducing the catalytic oxidation reaction liquid containing the flocculated sludge into an MBR tank, and carrying out separation deep treatment by a 0.2 mu m PTFE hollow fiber filtering membrane to obtain second sludge and final produced water, wherein the second sludge enters a sludge dewatering device for dewatering treatment, and the obtained dewatered sludge is transported to the outside for treatment.
The water quality in the above steps was monitored and the results are recorded in table 2.
Table 2 quality of produced water at each stage (unit: mg/L, pH dimensionless)
As can be seen from Table 2, the pretreatment, magnetic separation, catalytic oxidation and MBR multistage treatment method provided by the invention can effectively remove residual organic agents and heavy metal pollutants in wastewater, the operation cost is as low as 1 yuan/ton of water, and all indexes of the obtained final produced water are lower than III standard limit values in surface water environment quality standard (GB 3838-2002).
Example 2
The treatment system of the invention is used for treating wastewater of a lead-zinc concentrating plant in Guangxi river basin, and the quality of the concentrating wastewater is shown in table 3:
TABLE 3 quality of wastewater from certain lead-zinc concentrating mills (unit: mg/L, pH value dimensionless)
| Index of water quality | COD | pH | Cu | Zn | Cd | As | Pb |
| Content of | 584.2 | 6.58 | 0.841 | 21.634 | 0.100 | 1.449 | 5.277 |
The processing method comprises the following steps:
(1) The beneficiation wastewater is led into a collecting tank for collection;
(2) Collecting liquid of mineral separation wastewater with 200m 3 The flow of/h is led into a pretreatment tank, and 50mg/L of Na is added into the pretreatment tank through a first chemical adding device 2 S, stirring and mixing for 10min to obtain pretreated water;
(3) Introducing the pretreated water into a primary sedimentation Chi Jingzhi for sedimentation for 30min to obtain supernatant and first sludge, and allowing the first sludge to enter a sludge dewatering device for dewatering treatment to obtain dewatered sludge for outward transportation treatment;
(4) The supernatant liquid enters into the filler to be SiO 2 -Fe 3 O 4 The magnetic separation reactor of the composite material stays for 20min to obtain the water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reactor is introduced into the catalytic oxidation reaction tank, and H is respectively added to the front end of the catalytic oxidation reaction tank through the second chemical adding device and the third chemical adding device 2 O 2 100mg/L and FeSO 4 500mg/L, carrying out catalytic oxidation reaction;
(6) The catalytic oxidation reaction liquid obtained in the step (5) flows to the tail end of the catalytic oxidation reaction tank, firstly NaOH is added into a reaction zone through a fourth dosing device, the pH value of the reaction liquid is regulated to 7-8, and then 75mg/L of PAM is added into the reaction zone through a fifth dosing device, so that the catalytic oxidation reaction liquid containing flocculated sludge is obtained;
(7) Introducing the catalytic oxidation reaction liquid containing the flocculated sludge into an MBR tank, and carrying out separation deep treatment by a 0.1 mu m PTFE hollow fiber filtering membrane to obtain second sludge and final produced water, wherein the second sludge enters a sludge dewatering device for dewatering treatment, and the obtained dewatered sludge is transported to the outside for treatment.
The water quality in the above steps was monitored and the results are recorded in table 4.
Table 4 quality of produced water at each stage (unit: mg/L, pH dimensionless)
As can be seen from Table 4, the wastewater of this example has higher concentration COD and low concentration heavy metal, and the residual organic medicament and heavy metal pollutant in the wastewater can be effectively removed by controlling the parameters of the invention, the running cost is 2 yuan/ton of water, and the indexes of the obtained final produced water are all lower than the class III standard limit value in the surface water environment quality standard (GB 3838-2002).
Example 3
The treatment system of the invention is used for treating the wastewater of a lead-zinc concentrating plant in Cenzea, and the quality of the concentrating wastewater is shown in Table 5:
TABLE 5 quality of wastewater from certain lead-zinc concentrating mills (unit: mg/L, pH value dimensionless)
| Index of water quality | COD | pH value of | Cu | Zn | Cd | As | Pb |
| Content of | 896.4 | 4.63 | 15.77 | 29.39 | 13.45 | 36.2 | 50.11 |
The processing method comprises the following steps:
(1) The beneficiation wastewater is led into a collecting tank for collection;
(2) Concentrating the wastewater collection liquid at 150m 3 The flow of/h is led into a pretreatment tank, and 150mg/L Na is added into the pretreatment tank through a first chemical adding device 2 S, stirring and mixing for 30min to obtain pretreated water;
(3) Introducing the pretreated water into a primary sedimentation Chi Jingzhi for sedimentation for 30min to obtain supernatant and first sludge, and allowing the first sludge to enter a sludge dewatering device for dewatering treatment to obtain dewatered sludge for outward transportation treatment;
(4) The supernatant liquid enters into the filler to be SiO 2 -Fe 3 O 4 The magnetic separation reactor of the composite material stays for 60min to obtain the water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reactor is introduced into the catalytic oxidation reaction tank, and H is respectively added to the front end of the catalytic oxidation reaction tank through the second chemical adding device and the third chemical adding device 2 O 2 200mg/L and FeSO 4 600mg/L, carrying out catalytic oxidation reaction;
(6) The catalytic oxidation reaction liquid obtained in the step (5) flows to the tail end of the catalytic oxidation reaction tank, firstly NaOH is added into a reaction zone through a fourth dosing device, the pH value of the reaction liquid is regulated to 7-8, and then 100mg/L of PAM is added into the reaction zone through a fifth dosing device, so that the catalytic oxidation reaction liquid containing flocculated sludge is obtained;
(7) Introducing the catalytic oxidation reaction liquid containing the flocculated sludge into an MBR tank, and carrying out separation deep treatment by a 0.1 mu m PTFE hollow fiber filtering membrane to obtain second sludge and final produced water, wherein the second sludge enters a sludge dewatering device for dewatering treatment, and the obtained dewatered sludge is transported to the outside for treatment.
The water quality in the above steps was monitored and the results are recorded in table 6.
Table 6 quality of produced water at each stage (unit: mg/L, pH dimensionless)
| Index of water quality | COD | pH value of | Cu | Zn | Cd | As | Pb |
| Raw water | 896.4 | 4.63 | 15.77 | 29.39 | 13.45 | 36.2 | 50.11 |
| Primary sedimentation tank | 855.2 | 4.62 | 10.24 | 15.82 | 12.89 | 32.4 | 38.94 |
| Water produced by magnetic separation reactor | 807.9 | 4.87 | 0.61 | 0.74 | 0.01 | 0.27 | 0.58 |
| Catalytic oxidation reaction tank produced water | 18.33 | 7.59 | 0.58 | 0.52 | 0.002 | 0.04 | 0.03 |
| Final water production | 9.32 | 7.6 | 0.46 | 0.51 | 0.002 | 0.031 | 0.03 |
As can be seen from Table 6, the wastewater of this example has extremely high concentration of COD and heavy metal pollutants, and the residual organic agent and heavy metal pollutants in the wastewater can be effectively removed by controlling the parameters of the invention, the running cost is 5.4 yuan/ton of water, and the indexes of the obtained final produced water are all lower than the class III standard limit value in the surface water environment quality standard (GB 3838-2002).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A high COD lead zinc industrial beneficiation wastewater treatment system comprises a collecting tank;
the inlet of the pretreatment tank is communicated with the outlet of the collection tank, and the pretreatment tank is also communicated with a first dosing device which is used for adding soluble sulfides into the pretreatment tank;
the inlet of the primary sedimentation tank is communicated with the outlet of the pretreatment tank, and the primary sedimentation tank is provided with a first clear liquid outlet and a first sludge outlet;
the inlet is communicated with the first clear liquid outlet, and Fe is arranged in the magnetic separation reactor 3 O 4 A base filler; the Fe is 3 O 4 The base filler is TiO 2 -Fe 3 O 4 Composite material, siO 2 -Fe 3 O 4 Composite material and graphene-Fe 3 O 4 One of the composite materials, the Fe 3 O 4 In the base filler, fe 3 O 4 The mass percentage of (2) is 50-70%;
the inlet is communicated with the outlet of the magnetic separation reactor, a second dosing device and a third dosing device are arranged at the front end of the catalytic oxidation reaction tank, a fourth dosing device and a fifth dosing device are sequentially arranged at the tail end of the catalytic oxidation reaction tank, the second dosing device is used for adding an oxidant into the catalytic oxidation reaction tank, and the third dosing device is used for adding Fe into the catalytic oxidation reaction tank 2+ The fourth dosing device is used for adding an alkali reagent into the catalytic oxidation reaction tank, and the fifth dosing device is used for adding a coagulant aid into the catalytic oxidation reaction tank;
an inlet of the MBR tank is communicated with an outlet of the catalytic oxidation reaction tank, and a hollow fiber membrane is arranged in the MBR tank; the MBR tank is also provided with a second clear liquid outlet and a second sludge outlet; the hollow fiber membrane is made of PTFE or PVDF, and the pore diameter of the membrane is 0.1-0.5 mu m;
and the inlet is communicated with the first sludge outlet and the second sludge outlet, and the sludge dewatering device is provided with a third sludge outlet.
2. The treatment system of claim 1, wherein the readily soluble sulfide is Na 2 S、K 2 S and Li 2 One of S.
3. The treatment system of claim 1, wherein the oxidant is one of hydrogen peroxide, potassium persulfate and sodium persulfate, and the mass fraction of the hydrogen peroxide is 25% -30%;
the Fe is 2+ The base catalyst is soluble ferrous salt;
the alkali reagent is CaO, naOH and Ca (OH) 2 One or more of the following;
the coagulant aid is polyacrylamide.
4. A method for treating high-COD lead-zinc industrial beneficiation wastewater based on the treatment system of any one of claims 1 to 3, comprising the following steps:
(1) The high COD lead and zinc industrial beneficiation wastewater enters a collecting tank for collection;
(2) Inputting the beneficiation wastewater in the collecting tank into a pretreatment tank, and stirring, mixing and pretreating the beneficiation wastewater and soluble sulfides added by the first dosing device to obtain pretreated water;
(3) The pretreated water enters a primary sedimentation tank for standing and sedimentation to obtain supernatant and first sludge, and the first sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge;
(4) The supernatant enters a magnetic separation reactor for heavy metal adsorption separation to obtain water produced by the magnetic separation reactor;
(5) The water produced by the magnetic separation reaction enters the front end of the catalytic oxidation reaction tank and is added with the oxidant added by the second chemical adding device and the Fe added by the third chemical adding device 2+ Mixing the base catalysts, and carrying out catalytic oxidation reaction to obtain catalytic oxidation reaction liquid;
the catalytic oxidation reaction liquid flows to the tail end of the catalytic oxidation reaction tank and is mixed with an alkaline reagent added by a fourth dosing device to obtain a catalytic oxidation reaction liquid with the pH value of 7-8;
mixing the catalytic oxidation reaction liquid with the pH value of 7-8 with a coagulant aid added by a fifth dosing device, and performing flocculation reaction to obtain a catalytic oxidation reaction liquid containing flocculated sludge;
(6) And the catalytic oxidation reaction liquid containing the flocculated sludge enters an MBR tank for membrane separation treatment to obtain second sludge and final effluent, and the second sludge enters a sludge dewatering device for dewatering treatment to obtain dewatered sludge.
5. The method according to claim 4, wherein the COD content in the high COD lead-zinc industrial beneficiation wastewater is 200-1000 mg/L.
6. The method according to claim 4, wherein the effluent flow of the beneficiation wastewater in the collecting tank is 4000-6000 m 3 /d。
7. The method of claim 4, wherein the amount of soluble sulfide added is 50-150 mg/L; the retention time of the beneficiation wastewater in the pretreatment tank is 10-30 min;
and (3) standing and precipitating for 30-60 min.
8. The method according to claim 4, wherein the supernatant in step (4) has a residence time of 30 to 60 minutes in the magnetic separation reactor.
9. The method according to claim 4, wherein the amount of the oxidizing agent added is 100-200 mg/L; the Fe is 2+ The adding amount of the base catalyst is 400-600 mg/L; the addition amount of the coagulant aid is 50-100 mg/L; the residence time of the water produced by the magnetic separation reaction in the catalytic oxidation reaction tank is 20-120 min.
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