CN218811188U - Zinc-nickel-containing wastewater recycling treatment system - Google Patents
Zinc-nickel-containing wastewater recycling treatment system Download PDFInfo
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Abstract
The utility model discloses a zinc nickel waste water resourceful treatment system that contains, mix flocculation tank, the high-efficient sedimentation tank of one-level, second grade pH adjustment tank, second grade mixture flocculation tank, the high-efficient sedimentation tank of second grade including waste water equalizing basin, one-level pH adjustment tank, one-level, mud reservoir, plate and frame filter press, multi-media filter, ultrafiltration, weak acid cation resin, reverse osmosis unit, MVR evaporative concentration crystallization device, freezing melting crystallization device. The scheme of the utility model can ensure that the water quality of the discharged water can reach the water quality index of industrial water, meet the purpose of wastewater reuse and can recover zinc mud and anhydrous sodium sulphate with higher purity. The utility model discloses a scheme treatment effect is stable, and equipment automation degree of operation is high, and the operation is simple and convenient.
Description
Technical Field
The utility model belongs to the technical field of the water treatment technique and specifically relates to a zinc-nickel-containing wastewater resourceful treatment system is related to.
Background
In recent years, the economy of China is rapidly developed, and industrial production enters a vigorous development stage. The economic benefit is created and simultaneously the increasingly intensified environmental problem is accompanied. The wastewater recycling treatment is the necessary way to realize the sustainable development of industrial production and the win-win of economy and environment.
The cold-rolled sheet is subjected to oil removal and acid cleaning and then is treated by an electrolytic process to realize a surface coating. After electroplating, the surface of the cold-rolled plate needs to be cleaned, and the cleaning waste liquid is generally electroplating liquid with lower concentration. The cold rolling zinc-nickel-containing wastewater is electroplating cleaning waste liquid, has relatively fixed components, mainly comprises zinc sulfate and nickel sulfate, and also contains a small amount of pollutants such as iron ions, calcium ions, chloride ions, oils and the like.
The traditional treatment scheme of the cold rolling zinc-nickel-containing wastewater adopts a lime precipitation process, heavy metals of zinc and nickel are changed into hydroxide precipitates, solid-liquid separation is carried out in a sedimentation tank or a tubular microfiltration membrane, sludge is sent into a plate-and-frame filter press for dehydration treatment, and the sludge is treated as hazardous waste. The traditional treatment method has a good effect of removing metal ions, but the adding cost of the medicament is high, ions need to be additionally added into the existing wastewater, the conductivity and hardness of the wastewater are improved, the advanced treatment of the wastewater in the later period is not facilitated, the sludge production amount is large, secondary pollution is caused, and the waste of resources is caused.
In order to realize the sustainable development of enterprises and enable resources to be efficiently and circularly utilized, a recycling treatment scheme for cold-rolled zinc-nickel-containing wastewater is urgently needed.
It is to be noted that the information disclosed in this background section is only for enhancement of understanding of the general background of the invention, and should not be taken as an acknowledgement or any form of suggestion that this information constitutes prior art already known to a person skilled in the art.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a zinc-nickel-containing waste water resourceful treatment system for solve among the prior art traditional processing scheme of zinc-nickel-containing waste water and cause secondary pollution easily and the wasting of resources is serious.
In order to solve the technical problem, the utility model provides a zinc-nickel-containing wastewater recycling treatment system, which comprises a wastewater adjusting tank, a primary pH adjusting tank, a primary mixed flocculation tank, a primary high-efficiency sedimentation tank, a secondary pH adjusting tank, a secondary mixed flocculation tank, a secondary high-efficiency sedimentation tank, a sludge storage tank, a plate and frame filter press, a final neutralization tank, a multi-medium filter, an ultrafiltration device, weak acid cation resin, a reverse osmosis device, an MVR evaporation crystallization device, a freezing and melting crystallization device and a miscellaneous salt drying device;
the waste water adjusting tank is used for receiving waste water, so that the waste water is uniformly mixed in the waste water adjusting tank and is output to the primary pH adjusting tank;
the pH of the wastewater is adjusted to 7.5-8.0 by adding sodium hydroxide into the primary pH adjusting tank to form zinc hydroxide precipitate, and the wastewater is output to the primary mixed flocculation tank;
the primary mixed flocculation tank comprises polyferric oxide and magnetic powder, the wastewater is coagulated with an anionic high molecular flocculant in the primary mixed flocculation tank to form large-particle flocs, and the wastewater is output to the primary high-efficiency sedimentation tank;
the primary high-efficiency sedimentation tank is used for separating solid and liquid of the wastewater, zinc-containing sludge partially reflows to the primary mixed flocculation tank through a reflow sludge pump, part of the zinc-containing sludge is discharged into a shearing machine and a magnetic powder collector through a residual sludge pump, the collected magnetic powder returns to the primary mixed flocculation tank, zinc hydroxide sludge is discharged into a zinc sludge storage tank, and the zinc hydroxide sludge is recycled after being dewatered by a plate and frame filter press and is output to the secondary pH adjustment tank;
the secondary pH adjusting tank is used for adjusting the pH of the wastewater to 9.5-10.0 by adding sodium hydroxide to form nickel hydroxide precipitate and outputting the wastewater to the secondary mixed flocculation tank;
the secondary mixed flocculation tank is used for adding sodium carbonate, adding a small amount of polyferric oxide and PAM according to the condition of floc particles, and outputting the wastewater to the secondary efficient sedimentation tank;
the secondary high-efficiency sedimentation tank is used for carrying out solid-liquid separation on the wastewater, the nickel-containing and calcium carbonate mixed sludge partially reflows to the secondary mixed flocculation tank through a reflowing sludge pump, and the wastewater is output to the final neutralization tank;
the sludge storage tank is used for receiving the mixed sludge, and the mixed sludge is dewatered by the plate-and-frame filter press and then transported to an outside for disposal;
the final neutralizing tank is used for adding sulfuric acid, adjusting the pH back to 6.5-7 and outputting to the multi-media filter;
the multi-medium filter and the ultrafiltration device are used for removing small-particle suspended matters, so that the SDI of the effluent is less than or equal to 3;
the weak acid cation resin is used for reducing the content of heavy metals in the wastewater;
the reverse osmosis device is used for reducing and concentrating the wastewater, and the produced water meets the industrial water reuse standard;
the MVR evaporation crystallization device is used for controlling the concentration of the discharged concentrated solution in the evaporation process, discharging the concentrated solution into a thickener, and dehydrating the concentrated solution through a centrifugal machine to obtain anhydrous sodium sulphate;
the freezing and melting crystallization device is used for reducing the amount of the impurity salt, mother liquor of the MVR evaporation crystallization device is sent into the freezing and melting crystallization device, the mother liquor is quickly reduced to minus 5 ℃ to 0 ℃ for crystallization, and sodium sulfate decahydrate solid is obtained after the discharged low-temperature crystal mush is filtered and dehydrated. Discharging sodium sulfate decahydrate into a sodium sulfate dissolving tank, melting and evaporating again, controlling the autolytic concentration to be 35-40% of sodium sulfate solution, and centrifugally dewatering to obtain anhydrous sodium sulfate;
the miscellaneous salt drying device is used for receiving the cold nitre liquid and transporting the miscellaneous salt.
Optionally, the bottom of the wastewater adjusting tank is provided with a perforated aeration pipe.
Optionally, the perforated aeration pipe is made of UPVC, perforations of the perforated aeration pipe are arranged in a 45-degree crossing manner with a vertical line downwards, and the aperture is 3mm.
Optionally, 10% sodium hydroxide is used as a pH adjusting agent in the first-stage pH adjusting tank.
Optionally, the primary mixed flocculation tank is used for adding magnetic powder and a coagulant, the concentration of the magnetic powder in the primary mixed flocculation tank is 8-12g/L, the adding amount of the magnetic powder is 200-500ppm, the coagulant is polyferric, the adding amount is 100-200 ppm, and the primary mixed flocculation tank is used for adding an anionic high-molecular flocculant, wherein the adding amount is 1-3ppm.
Optionally, part of sludge in the primary high-efficiency sedimentation tank flows back to the primary mixed flocculation tank, the amount of the returned sludge is 10-20m & lt 3 & gt/h, the residual sludge is lifted to a shearing machine through a pump, sludge flocs are destroyed and then sent to a magnetic drum recoverer, and magnetic powder is recovered and then returned to the primary mixed flocculation tank.
Optionally, a coagulant is added into the primary mixed flocculation tank, wherein the coagulant is polyferric, and the adding amount is 50-100 ppm. And adding sodium carbonate and an anionic high-molecular flocculant into the primary mixing flocculation tank, determining the adding amount of the sodium carbonate according to the hardness of inlet water, wherein the adding amount of the anionic high-molecular flocculant is 0.1-0.5 ppm.
Optionally, the final neutralization tank is adjusted back by using 10% dilute sulfuric acid, and the pH is controlled to be 6.5-7.
Optionally, the filter material of the multi-media filter is quartz sand and anthracite.
Optionally, the running time of the multi-media filter is 24 hours, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 10-15min.
Optionally, the ultrafiltration device employs external pressure ultrafiltration, dead-end filtration.
Optionally, the running time of the ultrafiltration device is 30min, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 5-6min.
Optionally, after the weak acid cation resin is saturated by adsorption, the weak acid cation resin is regenerated by using 4-5% sulfuric acid and 4-5% sodium hydroxide, and an adsorption solution returns to the wastewater adjusting tank.
Optionally, the reverse osmosis unit employs an anti-fouling reverse osmosis membrane.
Optionally, the MVR evaporation crystallization device adopts waste heat steam to evaporate, and the concentration of the discharged concentrated solution is controlled to be 20-25%.
Optionally, the miscellaneous salt drying device adopts a vacuum rake dryer or a roller dryer, the feed concentration is 25-30%, and the frozen crystallization concentrated cold nitre solution is treated.
Compared with the prior art, the utility model discloses following beneficial effect has:
1. the utility model provides a zinc-nickel-containing wastewater recycling treatment system, which has stable treatment effect and simple and convenient operation, ensures that the effluent meets the water quality standard of industrial water, the wastewater is completely recycled, and zinc hydroxide and anhydrous sodium sulphate with higher purity are recycled, thereby realizing the recycling utilization of the zinc-nickel-containing wastewater;
2. the utility model provides a zinc-nickel-containing wastewater recycling treatment system, which reduces the sludge production as much as possible and reduces the treatment cost of hazardous wastes;
3. the utility model provides a zinc-nickel-containing wastewater resourceful treatment system realizes the waste water zero release, evaporates the evaporation mother liquor that will finally be a small amount and forms a small amount of miscellaneous salt, solidification treatment.
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Fig. 1 is the utility model discloses zinc-nickel containing waste water resourceful treatment system's that embodiment provided structural schematic.
Detailed Description
The following description of the embodiments of the present invention will be described in more detail with reference to the drawings. The advantages and features of the present invention will become more apparent from the following description. It should be noted that the drawings are in simplified form and are not to precise scale, and are provided for convenience and clarity in order to facilitate the description of the embodiments of the present invention.
In the description of the present invention, it should be understood that the terms "center", "upper", "lower", "left", "right", and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Referring to fig. 1, an embodiment of the present invention provides a system for recycling wastewater containing zinc and nickel, including a wastewater adjusting tank, a first-stage pH adjusting tank, a first-stage mixing flocculation tank, a first-stage high-efficiency sedimentation tank, a second-stage pH adjusting tank, a second-stage mixing flocculation tank, a second-stage high-efficiency sedimentation tank, a sludge storage tank, a plate-and-frame filter press, a final neutralization tank, a multi-media filter, an ultrafiltration apparatus, a weak acid cation resin, a reverse osmosis apparatus, an MVR evaporation crystallization apparatus, a freezing and melting crystallization apparatus, and a miscellaneous salt drying apparatus;
the wastewater adjusting tank is used for receiving wastewater, so that the wastewater is uniformly mixed in the wastewater adjusting tank and is output to the primary pH adjusting tank;
the pH of the wastewater is adjusted to 7.5-8.0 by adding sodium hydroxide into the primary pH adjusting tank to form zinc hydroxide precipitate, and the wastewater is output to the primary mixed flocculation tank;
the primary mixed flocculation tank comprises polyferric oxide and magnetic powder, the wastewater is coagulated with an anionic high molecular flocculant in the primary mixed flocculation tank to form large-particle flocs, and the wastewater is output to the primary high-efficiency sedimentation tank;
the primary high-efficiency sedimentation tank is used for carrying out solid-liquid separation on the wastewater, zinc-containing sludge partially reflows to the primary mixed flocculation tank through a reflowing sludge pump, part of the zinc-containing sludge is discharged into a shearing machine and a magnetic powder collector through a residual sludge pump, the collected magnetic powder returns to the primary mixed flocculation tank, zinc hydroxide sludge is discharged into a zinc sludge storage tank, and the zinc hydroxide sludge is recycled after being dewatered by a plate and frame filter press and is output to the secondary pH adjustment tank;
the secondary pH adjusting tank is used for adjusting the pH of the wastewater to 9.5-10.0 by adding sodium hydroxide to form nickel hydroxide precipitate and outputting the wastewater to the secondary mixed flocculation tank;
the secondary mixed flocculation tank is used for adding sodium carbonate, adding a small amount of polyferric oxide and PAM according to the condition of floc particles, and outputting the wastewater to the secondary efficient sedimentation tank;
the secondary high-efficiency sedimentation tank is used for carrying out solid-liquid separation on the wastewater, the nickel-containing and calcium carbonate mixed sludge partially reflows to the secondary mixed flocculation tank through a reflowing sludge pump, and the wastewater is output to the final neutralization tank;
the sludge storage tank is used for receiving the mixed sludge, and the mixed sludge is dewatered by the plate-and-frame filter press and then transported to an outside for disposal;
the final neutralizing tank is used for adding sulfuric acid, adjusting the pH back to 6.5-7 and outputting to the multi-media filter;
the multi-medium filter and the ultrafiltration device are used for removing small-particle suspended matters, so that the SDI of the effluent is less than or equal to 3;
the weak acid cation resin is used for reducing the content of heavy metals in the wastewater;
the reverse osmosis device is used for reducing and concentrating the wastewater, and the produced water meets the industrial water reuse standard;
the MVR evaporation crystallization device is used for controlling the concentration of the discharged concentrated solution in the evaporation process, discharging the concentrated solution into a thickener, and dehydrating the concentrated solution through a centrifugal machine to obtain anhydrous sodium sulphate;
the freezing and melting crystallization device is used for reducing the amount of the impurity salt, mother liquor of the MVR evaporation crystallization device is fed into the freezing and melting crystallization device, the mother liquor is rapidly reduced to minus 5 ℃ to 0 ℃ for crystallization, and sodium sulfate decahydrate solid is obtained after the discharged low-temperature crystal slurry is filtered and dehydrated. Discharging sodium sulfate decahydrate into a sodium sulfate dissolving tank, melting and evaporating again, controlling the autolytic concentration to be 35-40% of sodium sulfate solution, and centrifugally dewatering to obtain anhydrous sodium sulfate;
the miscellaneous salt drying device is used for receiving the cold nitre liquid and transporting the miscellaneous salt.
Compared with the prior art, the utility model provides a zinc-nickel-containing wastewater resource treatment system, the treatment effect is stable, the operation is simple and convenient, the effluent meets the industrial water quality standard, the wastewater is completely recycled, and zinc hydroxide and anhydrous sodium sulphate with higher purity are recycled, thereby realizing the resource utilization of the zinc-nickel-containing wastewater; the production amount of sludge is reduced as much as possible, and the treatment cost of hazardous waste is reduced; the scheme of this application still can realize the waste water zero release, evaporates a small amount of evaporation mother liquor and forms a small amount of miscellaneous salt, solidification treatment finally.
Specifically, in the embodiment, the bottom of the wastewater adjusting tank is provided with a perforated aeration pipe.
Specifically, in this embodiment, the perforated aeration pipe is made of UPVC, and the perforations of the perforated aeration pipe are arranged to intersect the vertical line at an angle of 45 ° downward, and have an aperture of 3mm.
Specifically, in this embodiment, 10% sodium hydroxide is used as the pH adjusting agent in the first-stage pH adjusting tank.
Specifically, in this embodiment, the primary mixed flocculation tank is filled with magnetic powder and a coagulant, the magnetic powder in the primary mixed flocculation tank has a concentration of 8-12g/L, the magnetic powder is filled at 200-500ppm, the coagulant is polyferric, the filling amount is 100-200 ppm, and the primary mixed flocculation tank is filled with an anionic polymeric flocculant at 1-3ppm.
Specifically, in this embodiment, a part of sludge in the primary high-efficiency sedimentation tank flows back to the primary mixed flocculation tank, the amount of the returned sludge is 10-20m3/h, the residual sludge is lifted to the shearing machine through the pump, sludge flocs are destroyed and then sent to the magnetic drum recoverer, and magnetic powder is recovered and then returned to the primary mixed flocculation tank.
Specifically, in this embodiment, a coagulant is added into the first-stage mixing flocculation tank, the coagulant is polyferric, and the addition amount is 50-100 ppm. And adding sodium carbonate and an anionic high-molecular flocculant into the primary mixing flocculation tank, determining the adding amount of the sodium carbonate according to the hardness of inlet water, wherein the adding amount of the anionic high-molecular flocculant is 0.1-0.5 ppm.
Specifically, in this example, the final neutralization tank was adjusted back using 10% dilute sulfuric acid, and the pH was controlled to 6.5-7.
Specifically, in this embodiment, the filter material of the multi-media filter is quartz sand and anthracite.
Optionally, the running time of the multi-media filter is 24 hours, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 10-15min.
Specifically, in this embodiment, the ultrafiltration apparatus employs external pressure type ultrafiltration, dead-end filtration.
Specifically, in the embodiment, the running time of the ultrafiltration device is 30min, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 5-6min.
Specifically, in this embodiment, after the weak acid cation resin is saturated by adsorption, 4-5% sulfuric acid and 4-5% sodium hydroxide are used for regeneration, and the adsorption solution is returned to the wastewater conditioning tank.
Specifically, in this embodiment, the reverse osmosis apparatus employs an anti-pollution reverse osmosis membrane.
Specifically, in this embodiment, the MVR evaporation crystallization device evaporates by using waste heat steam, and controls the concentration of the discharged concentrated solution to be 20 to 25%.
Specifically, in this embodiment, the miscellaneous salt drying device adopts a vacuum rake dryer, the feeding concentration is 25-30%, and the frozen crystallization concentrated cold nitre solution is treated.
Aiming at the water quality characteristics of cold rolling zinc-nickel-containing wastewater, the embodiment provides a process system suitable for recycling the zinc-nickel-containing wastewater, the treatment effect of the scheme is stable, the wastewater can be recycled completely, and zinc hydroxide and anhydrous sodium sulphate with higher purity are recycled, so that the resource utilization of the zinc-nickel-containing wastewater is realized. The equipment has high automation operation degree, is simple and convenient to operate and operate, and is suitable for industrial production.
The method comprises the following specific steps:
the parameters of the zinc-nickel containing wastewater are assumed as follows: pH is 1-3, total oil is less than or equal to 3mg/L, suspended matter is less than or equal to 200mg/L, COD is less than or equal to 30mg/L, hardness is less than or equal to 200mg/L, zn 2+ ≤8000mg/L，Ni 2+ ≤100mg/L，SO 4 2- ≤8000mg/L，C l- ≤50mg/L，TDS≤15000mg/L。
The treatment process comprises the following steps: the system comprises a wastewater adjusting tank, a primary pH adjusting tank, a primary mixed flocculation tank, a primary high-efficiency sedimentation tank, a secondary pH adjusting tank, a secondary mixed flocculation tank, a secondary high-efficiency sedimentation tank, a sludge storage tank, a plate-and-frame filter press, a multi-media filter, an ultrafiltration device, weak acid cation resin, a reverse osmosis device, an MVR evaporative crystallization device, a freezing and melting crystallization device and a miscellaneous salt drying device.
(1) A wastewater adjusting tank: the wastewater is discharged into a wastewater adjusting tank, and a perforated aeration pipe is arranged at the bottom of the tank to ensure that the incoming water is uniformly mixed in the adjusting tank; the bottom of the adjusting tank is provided with a perforated aeration pipe made of UPVC, the perforations are arranged downwards and form 45-degree cross arrangement with the vertical line, and the aperture is 3mm.
(2) Primary neutralization coagulation flocculation: the wastewater is lifted to a first-stage pH adjusting tank, and the pH is adjusted to 7.5-8.0 by adding sodium hydroxide to form zinc hydroxide precipitate. The wastewater automatically flows to a coagulation tank, added with polyferric oxide and magnetic powder, discharged into the flocculation tank and coagulated with an anionic polymeric flocculant (PAM) to form large-particle flocs. 10% sodium hydroxide is used as pH regulating agent, and the pH of the first-stage pH regulating tank is controlled to be 7.5-8.0. And adding magnetic powder and a coagulant into the primary coagulation tank, wherein the concentration of the magnetic powder in the coagulation tank is 8-12g/L, and the adding amount of the magnetic powder is 200-500ppm. The coagulant is polyferric, and the adding amount is 100-200 ppm. And adding an anionic high-molecular flocculant into the flocculation tank, wherein the adding amount is 1-3ppm.
(3) First-stage efficient precipitation: the wastewater automatically flows into a first-level efficient sedimentation tank for solid-liquid separation, the zinc-containing sludge partially flows back into a flocculation tank through a return sludge pump, part of the zinc-containing sludge is discharged into a shearing machine and a magnetic powder collector through a residual sludge pump, and the collected magnetic powder returns to a coagulation tank. And discharging the zinc hydroxide sludge into a zinc sludge storage pool, dehydrating by using a plate-and-frame filter press, and recycling. Part of sludge in the first-stage efficient sedimentation tank flows back to the flocculation tank, and the amount of the returned sludge is generally 10-20m & lt 3 & gt/h; and lifting the residual sludge to a shearing machine through a pump, damaging sludge flocs, sending the sludge flocs to a magnetic drum recoverer, and recovering magnetic powder and returning the sludge flocs to a coagulation tank. The recovery rate of the magnetic powder is more than or equal to 95 percent. Zinc hydroxide sludge is discharged into a zinc sludge storage tank, is dehydrated by a plate-and-frame filter press and then is recycled, and zinc sludge cakes can also be sent into a sludge drying device, so that the water content of the sludge is further reduced, and the sludge is convenient to transport outside at the later stage.
(4) Secondary neutralization coagulation flocculation: and (3) flowing the supernatant of the first-stage efficient precipitation to a second-stage pH adjusting tank, and adding sodium hydroxide to adjust the pH to 9.5-10.0 to form nickel hydroxide precipitation. The wastewater flows to a mixing flocculation tank automatically, sodium carbonate is added, and a small amount of polyferric oxide and PAM are added according to the condition of floc particles. And automatically flowing into a secondary efficient sedimentation tank for solid-liquid separation. The pH value of the second-stage pH adjusting tank is controlled to be 9.5-10.0. And (3) adding a coagulant into the secondary coagulation tank, wherein the coagulant is polyferric and the adding amount is 50-100 ppm. Sodium carbonate and anionic high molecular flocculant are added into the flocculation tank. The adding amount of sodium carbonate is determined according to the hardness of inlet water, and the adding amount of the anionic polymeric flocculant is 0.1-0.5 ppm.
(5) Secondary efficient precipitation: effluent from the second-stage neutralization coagulation flocculation tank automatically flows into a second-stage efficient sedimentation tank for solid-liquid separation, and the mixed sludge containing nickel and calcium carbonate partially flows back into the flocculation tank through a return sludge pump, so that the dosage of the medicament is reduced. Discharging the mixed sludge into a mixed sludge storage tank, dehydrating by a plate-and-frame filter press, and transporting outside.
(6) Final neutralization tank: the secondary high efficiency precipitated supernatant flows to a final neutralization tank where sulfuric acid is added to adjust the pH back to 6.5-7. And adjusting the pH value of the final neutralization tank to 6.5-7 by using 10% dilute sulfuric acid.
(7) Multi-media filter and ultrafiltration device: the precipitated effluent is lifted to a multi-media filter and an ultrafiltration device through a pump, and small-particle suspended matters are further removed, so that the effluent SDI is less than or equal to 3, and the requirement of reverse osmosis water inflow is met. The filter material of the multi-medium filter is quartz sand and anthracite. The running time is 24h, the air-water backwashing is carried out for 1 time, and the backwashing time is about 10-15min. The ultrafiltration device adopts external pressure type ultrafiltration and dead-end filtration. The running time is 30min, and the air-water backwashing time is about 5-6min after 1 time of backwashing. According to the pollution condition, chemical strengthening cleaning is carried out regularly.
(8) Weak acid cation resin: the ultrafiltration effluent is lifted to a weak acid cation resin device to further reduce the heavy metal content (such as calcium, magnesium, zinc, nickel and the like) in the wastewater. After the weak acid cation resin is adsorbed and saturated, 4-5% sulfuric acid and 4-5% sodium hydroxide are adopted for regeneration, and the adsorption solution returns to a wastewater adjusting tank.
(9) A reverse osmosis device: and a secondary reverse osmosis device is arranged to reduce the amount of the wastewater and concentrate the wastewater, and the produced water meets the industrial water reuse standard. The reverse osmosis device adopts an anti-pollution reverse osmosis membrane, and the concentrated water TDS is concentrated to about 80g/L through secondary reverse osmosis;
(10) MVR evaporative crystallization: the reverse osmosis concentrated water promotes MVR evaporation crystallization system, the concentration (20-25%) of the concentrated solution discharged in the evaporation process is controlled, the concentrated solution is discharged into a thickener, and the anhydrous sodium sulphate is obtained by dewatering through a centrifuge. The condensed water meets the industrial water recycling standard for recycling. The MVR evaporation crystallization adopts waste heat steam for evaporation, the concentration of a discharged concentrated solution needs to be controlled to be 20-25%, and the centrifugal dehydration condition of anhydrous sodium sulfate is met; the content of chloride in the concentrated mother liquor is controlled to ensure the purity of anhydrous sodium sulphate. When the concentration of sodium chloride exceeds 15-18%, the mother liquor of MVR evaporation crystallization is continuously sent into a freezing crystallization system, rapidly reduced to-5-0 ℃, and dehydrated to form sodium sulfate decahydrate.
(11) Freezing, melting and crystallizing: in order to reduce the amount of impurity salt, mother liquor of MVR evaporation crystallization is continuously sent into a freezing crystallization system and is rapidly reduced to-5-0 ℃ for crystallization. And filtering and dehydrating the discharged low-temperature crystal mush to obtain sodium sulfate decahydrate solid. Discharging the sodium sulfate decahydrate into a sodium sulfate dissolving tank, melting and evaporating again, controlling the autolytic concentration to be (35-40%) sodium sulfate solution, and centrifugally dehydrating to obtain anhydrous sodium sulfate. And (5) sending the cold saltpeter liquid into a miscellaneous salt drying device to change into miscellaneous salt for outward transportation. The condensed water meets the industrial water recycling standard for recycling. The miscellaneous salt drying device adopts a vacuum rake dryer, the feeding concentration is 25-30%, and the frozen, crystallized, concentrated and cold nitre liquid is treated.
To facilitate a better understanding of the aspects of the present application by those skilled in the art, a more specific example is provided below:
the parameters of the wastewater containing zinc and nickel are the same as the assumed parameters. Zinc-nickel-containing waste water resourceful treatment system includes: the system comprises a wastewater adjusting tank, a primary pH adjusting tank, a primary mixed flocculation tank, a primary high-efficiency sedimentation tank, a secondary pH adjusting tank, a secondary mixed flocculation tank, a secondary high-efficiency sedimentation tank, a sludge storage tank, a plate-and-frame filter press, a multi-media filter, an ultrafiltration device, weak acid cation resin, a reverse osmosis device, an MVR evaporative crystallization device, a freezing and melting crystallization device and a miscellaneous salt drying device.
The pH value of the primary neutralization is 7.5-8, the polyferric oxide and magnetic powder are added into the primary coagulation tank, and the mixture is discharged into the flocculation tank to be coagulated with an anionic high molecular flocculant (PAM) to form large-particle flocs and form zinc hydroxide precipitate. The pH value of the secondary neutralization is 9.5-10, the poly-iron is added into a secondary coagulation tank, and the sodium carbonate and the anionic high molecular flocculant are added into a secondary flocculation tank to form nickel hydroxide and calcium carbonate precipitates.
And discharging sludge in the first-level efficient sedimentation tank into a shearing machine and a magnetic powder collector, and returning the collected magnetic powder to the coagulation tank. The recovery rate of the magnetic powder is more than or equal to 95 percent. And (3) discharging the zinc hydroxide sludge into a zinc sludge storage tank, dehydrating by using a plate-and-frame filter press, wherein the water content of the sludge cake is less than or equal to 70%, and in order to reduce the water content of the sludge, the sludge cake can be sent into a sludge drying device, so that the water content is less than or equal to 30%, and the transportation and the recycling are convenient. The sludge in the secondary efficient sedimentation tank is mixed sludge, the main components of which are nickel hydroxide and calcium carbonate, and the mixed sludge is transported outside after being dehydrated by a plate-and-frame filter press. The plate-and-frame filter presses of two different types of sludge are separately arranged, so that the purity of the zinc hydroxide sludge is ensured, and the recycling value is improved. Through analysis and detection, the zinc oxide content of the zinc hydroxide sludge after dehydration treatment is 75-85%, and the rest main impurities are ferric oxide and silicon dioxide (magnetic powder content).
The ultrafiltration device of the embodiment adopts external pressure type ultrafiltration, and the turbidity of the inlet water is preferably less than or equal to 5NTU, so that the front end adopts a multi-medium filter and a self-cleaning filter to intercept larger particle suspended matters. If submerged ultrafiltration is used, the front-end pretreatment can be relaxed appropriately.
The weak acid cation resin bed can adopt a fixed bed or a floating bed, the weak acid cation resin bed adopts the floating bed in the embodiment, and the designed filtration speed is less than or equal to 25-28m/h. In the regeneration process, 4-5% of sulfuric acid, 4-5% of sodium hydroxide and softened water are used for regeneration. Firstly, sulfuric acid is adopted for regeneration, and the regeneration flow rate is 2.3-2.5m/h; then water washing is adopted, and the flow rate of the water washing is 3-3.2m/h; sodium hydroxide is adopted for transformation, and the regeneration flow rate is 2.3-2.5m/h; finally, water washing is adopted, and the flow rate of the water washing is 3-3.2m/h.
The reverse osmosis device adopts an anti-pollution reverse osmosis membrane, the first-stage reverse osmosis is low-pressure reverse osmosis, the recovery rate is 60-70%, and concentrated water is concentrated to 35-40g/L; the second-stage reverse osmosis is high-pressure reverse osmosis, the recovery rate is 60-70%, and the TDS of the concentrated water is concentrated to 80-10g/L. The low-pressure reverse osmosis produced water and the high-pressure reverse osmosis produced water are mixed to be used as industrial reuse water, and the water quality meets the design specification of industrial circulating cooling water treatment (GB/T50050-2017).
The evaporative crystallization process section can select multi-effect evaporation under the condition of residual heat steam, thereby reducing the operation cost. In this embodiment, there is no residual heat vapor resource, and a mechanical compression evaporative crystallization process (MVR evaporative crystallization) is adopted. The concentration and temperature of the materials must be well controlled in the operation process so as to ensure the purity of the anhydrous sodium sulphate. The quality of the anhydrous sodium sulphate can meet the standards of class II first-class products in the standard table 1 of GB/T6009-2014.
Finally, the frozen, crystallized, concentrated and cold saltpeter liquid passes through a vacuum rake dryer to be transported out as miscellaneous salt.
Based on the same invention concept, the utility model also provides a zinciferous nickel waste water resource treatment method, utilize any one of above-mentioned feature description zinciferous nickel waste water resource treatment system, zinciferous nickel waste water resource treatment method includes:
the wastewater adjusting tank receives wastewater, so that the wastewater is uniformly mixed in the wastewater adjusting tank and is output to the primary pH adjusting tank;
the pH of the wastewater is adjusted to 7.5-8.0 by adding sodium hydroxide into the primary pH adjusting tank to form zinc hydroxide precipitate, and the wastewater is output to the primary mixed flocculation tank;
the primary mixed flocculation tank comprises polyferric oxide and magnetic powder, the wastewater is coagulated with an anionic high molecular flocculant in the primary mixed flocculation tank to form large granular flocs, and the wastewater is output to the primary high-efficiency sedimentation tank;
the primary high-efficiency sedimentation tank enables the wastewater to be subjected to solid-liquid separation, zinc-containing sludge partially reflows to the primary mixed flocculation tank through a reflowing sludge pump, part of the zinc-containing sludge is discharged into a shearing machine and a magnetic powder collector through a residual sludge pump, the collected magnetic powder returns to the primary mixed flocculation tank, zinc hydroxide sludge is discharged into a zinc sludge storage tank, the zinc hydroxide sludge is dehydrated through a plate and frame filter press and then recycled, and the wastewater is output to the secondary pH adjustment tank;
the secondary pH adjusting tank adjusts the pH of the wastewater to 9.5-10.0 by adding sodium hydroxide to form nickel hydroxide precipitate, and the wastewater is output to the secondary mixed flocculation tank;
the secondary mixed flocculation tank is used for adding sodium carbonate, adding a small amount of polyferric oxide and PAM according to the condition of floc particles, and outputting the wastewater to the secondary efficient sedimentation tank;
the secondary high-efficiency sedimentation tank is used for carrying out solid-liquid separation on the wastewater, part of the mixed sludge containing nickel and calcium carbonate flows back to the secondary mixed flocculation tank through a return sludge pump, and the wastewater is output to the final neutralization tank;
the sludge storage tank receives the mixed sludge, and the mixed sludge is dewatered by the plate-and-frame filter press and then transported to an outside for disposal;
adding sulfuric acid into the final neutralizing tank, adjusting the pH back to 6.5-7, and outputting to the multi-media filter;
the multi-medium filter and the ultrafiltration device remove small-particle suspended matters, so that the SDI of the effluent is less than or equal to 3;
the weak acid cation resin is used for reducing the content of heavy metals in the wastewater;
the reverse osmosis device reduces and concentrates the wastewater, and the produced water meets the industrial water reuse standard;
the MVR evaporation crystallization device discharges the discharged concentrated solution into a thickener by controlling the concentration of the discharged concentrated solution in the evaporation process, and dehydrates the concentrated solution through a centrifugal machine to obtain anhydrous sodium sulphate;
the freezing and melting crystallization device reduces the amount of impurity salt, mother liquor of the MVR evaporation crystallization device is sent into the freezing and melting crystallization device, the mother liquor is quickly reduced to minus 5 ℃ to 0 ℃ for crystallization, and sodium sulfate decahydrate solid is obtained after the discharged low-temperature crystal mush is filtered and dehydrated. Discharging sodium sulfate decahydrate into a sodium sulfate dissolving tank, melting and evaporating again, controlling the autolytic concentration to be 35-40% sodium sulfate solution, and centrifugally dewatering to obtain anhydrous sodium sulfate;
and the miscellaneous salt drying device receives the cold nitre liquid and turns into miscellaneous salt for outward transportation.
Compared with the prior art, the utility model discloses following beneficial effect has:
1. the utility model provides a zinc-nickel-containing wastewater recycling treatment system, which has stable treatment effect and simple and convenient operation, ensures that the effluent meets the water quality standard of industrial water, the wastewater is completely recycled, and zinc hydroxide and anhydrous sodium sulphate with higher purity are recycled, thereby realizing the recycling utilization of the zinc-nickel-containing wastewater;
2. the utility model provides a zinc-nickel-containing wastewater recycling treatment system, which reduces the sludge production as much as possible and reduces the treatment cost of hazardous wastes;
3. the utility model provides a zinc nickel-containing waste water resourceful treatment system realizes the waste water zero release, evaporates a small amount of evaporation mother liquor that will finally be a small amount and forms a small amount of miscellaneous salt, solidification treatment.
The utility model provides a zinc-nickel-containing wastewater resource treatment method, with zinc-nickel-containing wastewater resource treatment system belongs to same utility model and conceives, consequently, has the same beneficial effect, does not do here and give unnecessary details.
In the description of the present specification, reference to the description of "one embodiment," "some embodiments," "an example" or "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. And the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments. Furthermore, various embodiments or examples described in this specification can be combined and combined by those skilled in the art.
The above description is only for the preferred embodiment of the present invention, and does not limit the present invention. Any technical personnel who belongs to the technical field, in the scope that does not deviate from the technical scheme of the utility model, to the technical scheme and the technical content that the utility model discloses expose do the change such as the equivalent replacement of any form or modification, all belong to the content that does not break away from the technical scheme of the utility model, still belong to within the scope of protection of the utility model.
Claims (16)
1. A zinc-nickel-containing wastewater recycling treatment system is characterized by comprising a wastewater adjusting tank, a primary pH adjusting tank, a primary mixed flocculation tank, a primary high-efficiency sedimentation tank, a secondary pH adjusting tank, a secondary mixed flocculation tank, a secondary high-efficiency sedimentation tank, a sludge storage tank, a plate-and-frame filter press, a final neutralization tank, a multi-medium filter, an ultrafiltration device, a weak acid cation resin, a reverse osmosis device, an MVR evaporation crystallization device, a freezing and melting crystallization device and a mixed salt drying device;
the wastewater adjusting tank is used for receiving wastewater, so that the wastewater is uniformly mixed in the wastewater adjusting tank and is output to the primary pH adjusting tank;
the pH of the wastewater is adjusted to 7.5-8.0 by adding sodium hydroxide into the primary pH adjusting tank to form zinc hydroxide precipitate, and the wastewater is output to the primary mixed flocculation tank;
the primary mixed flocculation tank comprises polyferric oxide and magnetic powder, the wastewater is coagulated with an anionic high molecular flocculant in the primary mixed flocculation tank to form large granular flocs, and the wastewater is output to the primary high-efficiency sedimentation tank;
the primary high-efficiency sedimentation tank is used for separating solid and liquid of the wastewater, zinc-containing sludge partially reflows to the primary mixed flocculation tank through a reflow sludge pump, part of the zinc-containing sludge is discharged into a shearing machine and a magnetic powder collector through a residual sludge pump, the collected magnetic powder returns to the primary mixed flocculation tank, zinc hydroxide sludge is discharged into a zinc sludge storage tank, and the zinc hydroxide sludge is recycled after being dewatered by a plate and frame filter press and is output to the secondary pH adjustment tank;
the secondary pH adjusting tank is used for adjusting the pH of the wastewater to 9.5-10.0 by adding sodium hydroxide to form nickel hydroxide precipitate and outputting the wastewater to the secondary mixed flocculation tank;
the secondary mixed flocculation tank is used for adding sodium carbonate, adding a small amount of polyferric oxide and PAM according to the condition of floc particles, and outputting the wastewater to the secondary efficient sedimentation tank;
the secondary high-efficiency sedimentation tank is used for carrying out solid-liquid separation on the wastewater, the nickel-containing and calcium carbonate mixed sludge partially reflows to the secondary mixed flocculation tank through a reflowing sludge pump, and the wastewater is output to the final neutralization tank;
the mixed sludge storage tank is used for receiving mixed sludge, and the mixed sludge is dewatered by the plate-and-frame filter press and then transported to an outside for disposal;
the final neutralizing tank is used for adding sulfuric acid, adjusting the pH back to 6.5-7 and outputting to the multi-media filter;
the multi-medium filter and the ultrafiltration device are used for removing small-particle suspended matters, so that the SDI of the effluent is less than or equal to 3;
the weak acid cation resin is used for reducing the content of heavy metals in the wastewater;
the reverse osmosis device is used for reducing and concentrating the wastewater, and the produced water meets the industrial water reuse standard;
the MVR evaporation crystallization device is used for discharging the discharged concentrated solution into a thickener by controlling the concentration of the discharged concentrated solution in the evaporation process, and dehydrating the discharged concentrated solution through a centrifugal machine to obtain anhydrous sodium sulphate;
the freezing and melting crystallization device is used for reducing the amount of impurity salt, mother liquor of the MVR evaporation crystallization device is sent into the freezing and melting crystallization device to be rapidly reduced to minus 5 ℃ to 0 ℃ for crystallization, discharged low-temperature crystal mush is filtered and dehydrated to obtain sodium sulfate decahydrate solid, the sodium sulfate decahydrate is discharged into a sodium sulfate melting tank to be melted and evaporated again, the autolytic concentration is controlled to be 35-40% of sodium sulfate solution, and anhydrous sodium sulphate is obtained after centrifugal dehydration;
the miscellaneous salt drying device is used for receiving the cold nitre liquid and transporting the miscellaneous salt.
2. The recycling system for wastewater containing zinc and nickel according to claim 1, characterized in that the bottom of the wastewater adjusting tank is provided with a perforated aeration pipe.
3. The recycling treatment system for wastewater containing nickel and zinc according to claim 2, wherein the perforated aeration pipe is made of UPVC, the perforations of the perforated aeration pipe are arranged in a 45-degree crossing manner with the vertical line downwards, and the aperture is 3mm.
4. The recycling treatment system for wastewater containing nickel and zinc according to claim 1, wherein 10% sodium hydroxide is used as a pH adjusting agent in the first-stage pH adjusting tank.
5. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, characterized in that the primary mixing flocculation tank is fed with magnetic powder and coagulant, the magnetic powder in the primary mixing flocculation tank has a concentration of 8-12g/L, the magnetic powder is fed at 200-500ppm, the coagulant is polyferric, the feeding amount is 100-200 ppm, and the primary mixing flocculation tank is fed with anionic high molecular flocculant at 1-3ppm.
6. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein part of sludge in the primary high-efficiency sedimentation tank flows back into the primary mixed flocculation tank, the amount of the returned sludge is 10-20m3/h, the residual sludge is lifted to a shearing machine through a pump, sludge flocs are destroyed and then sent to a magnetic drum recoverer, and magnetic powder is recovered and then returned to the primary mixed flocculation tank.
7. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, characterized in that coagulant is added into the primary mixing flocculation tank, the coagulant is polyferric, the adding amount is 50-100 ppm, sodium carbonate and anionic polymeric flocculant are added into the primary mixing flocculation tank, the adding amount of the sodium carbonate is determined according to the hardness of inlet water, and the adding amount of the anionic polymeric flocculant is 0.1-0.5 ppm.
8. The recycling treatment system for waste water containing zinc and nickel according to claim 1, characterized in that the final neutralization tank is adjusted back by 10% dilute sulfuric acid, and the pH is controlled to 6.5-7.
9. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the filter material of the multi-media filter is quartz sand and anthracite.
10. The recycling treatment system for wastewater containing zinc and nickel according to claim 9, wherein the running time of the multi-media filter is 24h, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 10-15min.
11. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the ultrafiltration device adopts external pressure type ultrafiltration and dead-end filtration.
12. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the running time of the ultrafiltration device is 30min, the air-water backwashing is performed for 1 time, and the air-water backwashing time is 5-6min.
13. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the weak acid cation resin is regenerated by using 4-5% sulfuric acid and 4-5% sodium hydroxide after being saturated by adsorption, and the adsorption solution returns to the wastewater adjusting tank.
14. The recycling treatment system for waste water containing zinc and nickel according to claim 1, characterized in that the reverse osmosis device adopts an anti-pollution reverse osmosis membrane.
15. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the MVR evaporation crystallization device adopts waste heat steam to evaporate, and the concentration of discharged concentrated solution is controlled to be 20-25%.
16. The recycling treatment system for wastewater containing zinc and nickel according to claim 1, wherein the miscellaneous salt drying device adopts a vacuum rake dryer or a roller dryer, the feed concentration is 25-30%, and the frozen crystalline concentrated cold nitrate solution is treated.
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