CN107226581B

CN107226581B - Zinc-containing wastewater treatment method, treatment system and application

Info

Publication number: CN107226581B
Application number: CN201710446978.4A
Authority: CN
Inventors: 韩全; 张恒
Original assignee: Guangdong Yeanovo Environmental Protection Co ltd
Current assignee: Guangdong Shangchen Environmental Technology Co ltd
Priority date: 2017-06-14
Filing date: 2017-06-14
Publication date: 2020-08-28
Anticipated expiration: 2037-06-14
Also published as: CN107226581A

Abstract

The invention provides a zinc-containing wastewater treatment method, which is characterized by sequentially comprising the following steps: (1) pretreating zinc-containing wastewater to obtain pretreated water; (2) performing biochemical treatment on the pretreated water obtained in the step (1) to obtain biochemical treated water; (3) concentrating the biochemical treatment water obtained in the step (2) to obtain concentrated high-salinity concentrated water and reuse water; (4) carrying out evaporation crystallization treatment on the concentrated high-salinity concentrated water obtained in the step (3) to obtain recycled water and crystals; wherein the standard of the recycled water is as follows: the pH value is 6-8, the conductivity is less than or equal to 50, the COD is less than or equal to 30, and the turbidity is less than or equal to 1; the method has the advantages of simple operation, stable operation, low cost and high treatment efficiency, thereby achieving zero discharge or low discharge of the zinc-containing wastewater in the electroplating production and simultaneously realizing recovery of each metal ion in the wastewater with higher purity.

Description

Zinc-containing wastewater treatment method, treatment system and application

Technical Field

The invention relates to a method and a system for treating wastewater, in particular to a method for treating zinc-containing wastewater in the electroplating industry, a system for treating the zinc-containing wastewater in the electroplating industry, which is already used for the method, and application of the method or the system in treating the zinc-containing wastewater in the electroplating industry.

Background

The zinc-containing electroplating wastewater treatment process usually adopts a chemical method, an electrolytic method, a common ion exchange method and other treatment methods. The above treatment methods have certain limitations and cannot achieve zero emission. The chemical method is a widely used method for treating the complexing electroplating wastewater at present, a large amount of acid and alkali are required to be added in the production process, and simultaneously, ferrous sulfate and polyaluminium chloride are required to be added, so that the salt content of the discharged water is increased, and the residual metal ions in the water still cannot reach the discharge standard; because the content of the controlled substances specified by the wastewater discharge standard is extremely low, excessive chemicals are required to be added to reach the discharge standard, the cost is high, and the wastewater cannot be recycled as process water; the electrolytic method has mature treatment process and stable operation, but because the content of controlled substances specified by the discharge standard is extremely low, the power consumption is large during the electrolysis of the wastewater, the treatment cost is high, toxic gas is easy to generate, and the wastewater is difficult to treat and discharge after reaching the standard; the common ion exchange method adopts organic framework ion exchange resin to effectively remove various harmful ions in the wastewater, and simultaneously water can be recycled, but the resin consumption is large, the treatment of the regenerated liquid is difficult, a large amount of acid and alkali are consumed, and the treatment cost is high; in addition, during the regeneration of the resin, the resin is largely broken due to the regeneration, shrinkage and expansion of the resin, and the economic efficiency is not high. Some treatment methods adopt reverse osmosis membrane concentration to treat electroplating wastewater and simultaneously recycle pure water, but the process cannot meet the process requirements and has limitation in use.

It can be seen that various treatment methods for wastewater containing zinc at present have many problems, even if the existing equipment of each electroplating plant is fully utilized, most or all of the wastewater cannot be recycled, and valuable metals in the wastewater cannot be effectively separated and recovered.

Disclosure of Invention

The invention aims to overcome the problems and defects in the prior art and provide a zinc-containing wastewater treatment method and a corresponding treatment system which are simple to operate, stable to operate, low in cost and high in treatment efficiency, so that zero emission or low emission of zinc-containing wastewater in electroplating production is achieved, high-purity recovery of metal ions in the wastewater is realized, the production water consumption in the electroplating industry is saved, the pollution of the electroplating industry to the environment is remarkably reduced, the use amount of acid and alkali is reduced, resources can be effectively saved, the production cost is reduced, the recovery of equipment investment is realized, and the clean production and sustainable development of the electroplating industry are promoted and promoted.

The purpose of the invention is realized by the following technical scheme:

the invention provides a zinc-containing wastewater treatment method, which is characterized by sequentially comprising the following steps:

(1) pretreating zinc-containing wastewater to obtain pretreated water;

(2) performing biochemical treatment on the pretreated water obtained in the step (1) to obtain biochemical treated water;

(3) concentrating the biochemical treatment water obtained in the step (2) to obtain concentrated high-salinity concentrated water and reuse water;

(4) carrying out evaporation crystallization treatment on the concentrated high-salinity concentrated water obtained in the step (3) to obtain recycled water and crystals;

wherein the standard of the recycled water is as follows: pH 6-8, conductivity less than or equal to 50, COD less than or equal to 30 and turbidity less than or equal to 1.

Preferably, in the step (1),

the zinc-containing wastewater has pH of 6-8 and contains pollutants such as zinc ions, SS, COD and the like; wherein Zn in the zinc-containing wastewater²⁺Is 30-50 mg/L;

preferably, the step of pre-treating is:

(1-1) introducing the zinc-containing wastewater into a zinc breaking tank, adding sulfuric acid into the zinc breaking tank until the pH value is 2-3, and then adding sodium hypochlorite until the ORP value is 300-400mv to carry out zinc breaking reaction;

(1-2) introducing the wastewater treated in the step (1-1) into a pH adjusting tank, and adding sodium hydroxide until the pH is 8.5-9.5;

(1-3) introducing the wastewater treated in the step (1-2) into a chemical reaction tank, adding a coagulant, then adding a flocculant, and stirring for 20-30 min;

(1-4) introducing the wastewater treated in the step (1-3) into a precise control efficient precipitation system;

preferably, in the step (1-1), a 10% sulfuric acid solution is added to adjust the pH; preferably, sodium hypochlorite solution with the concentration of 10 percent is added to adjust the ORP value;

preferably, the zinc breaking reaction time of the step (1-1) is 20-30 min;

preferably, in the step (1-2), a sodium hydroxide solution with the concentration of 10% is added to adjust the pH;

preferably, in the step (1-3), the coagulant is an inorganic coagulant, more preferably PAC; preferably, the flocculant is an organic flocculant, more preferably PAM; preferably, the time interval between the addition of the coagulant and the flocculant is 20-40 min;

preferably, the pH of the wastewater treated by the step (1-3) is 8-9;

preferably, in the step (1-4), the precise control efficient sedimentation system is formed by sequentially connecting a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge hopper; preferably, the wastewater treated in the step (1-3) is sequentially introduced into the water distribution system, the sedimentation treatment tank and the inclined pipe; the supernatant after the treatment enters an effluent weir to obtain pretreated water, and the obtained sludge is deposited in a sludge hopper; preferably, the pressure of the sedimentation treatment tank is 2-3 Mpa.

Preferably, in the step (2), the biochemical treatment step is: sequentially feeding the pretreated water obtained in the step (1) into an anaerobic tank, an aerobic tank and a membrane bioreactor;

preferably, the anaerobic pool comprises anaerobic bacteria; preferably, the anaerobic bacteria are selected from one or more of yeast, nitrate bacteria, clostridium or bacteroides;

preferably, the yeast, nitrate, clostridia or bacteroides are acclimatized to be salt-tolerant;

preferably, the aerobic tank contains aerobic microorganisms;

preferably, the aerobic microorganism is selected from one or more of bacillus, rhizobium, nitrobacteria or mould;

preferably, the bacillus, rhizobium, nitrifier or mould is acclimated to be salt tolerant;

preferably, the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool; preferably, the hollow fiber membrane module is located in the membrane tank;

preferably, the pore diameter of the hollow fiber membrane is 0.01-0.1 μm;

preferably, the pH after the biochemical treatment is 6 to 8.

Preferably, in the step (3), the concentration treatment step is: sequentially passing the biochemical treatment water obtained in the step (2) through a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system;

preferably, the primary nanofiltration system is formed by sequentially connecting a precision filter and a primary nanofiltration membrane;

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the filter element pore size of the precise microporous filter is 5 μm;

preferably, the primary nanofiltration membrane is an industrial grade high-desalination-rate nanofiltration membrane;

preferably, the aperture of the primary nanofiltration membrane is 1-2 nm;

preferably, the rejection rate of the primary nanofiltration membrane to sodium ions is 50-70%;

preferably, the rejection rate of the primary nanofiltration membrane on heavy metal ions and salts is more than 97%;

preferably, the membrane feeding pressure of the primary nanofiltration system is 1.0-1.5 Mpa;

preferably, the relative molecular mass cut-off range of the primary nanofiltration system is 150-300 daltons;

preferably, the pH of the water entering the primary nanofiltration system is 6-8;

preferably, the permeate of the primary nanofiltration system can be used as reuse water;

preferably, the concentrated solution of the primary nanofiltration system enters a primary reverse osmosis system.

Preferably, in the step (3), the first-stage reverse osmosis system is formed by sequentially connecting a precision filter and a first-stage reverse osmosis membrane;

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the first-stage reverse osmosis membrane is a brackish water reverse osmosis membrane;

preferably, the rejection rate of the first-stage reverse osmosis membrane on heavy metal ions and salts is more than 98 percent;

preferably, the aperture of the primary reverse osmosis membrane is 0.1-1 nm;

preferably, the membrane inlet pressure of the primary reverse osmosis system is 1.8 Mpa;

preferably, the pH of the water entering the primary reverse osmosis system is 5-6;

preferably, the primary reverse osmosis system is adjusted in pH by adding hydrochloric acid;

preferably, hydrochloric acid with the concentration of 0.2-0.5% is added to adjust the pH;

preferably, the permeate of the primary reverse osmosis system returns to the primary nanofiltration system;

preferably, the concentrate of the primary reverse osmosis system enters a secondary reverse osmosis system.

Preferably, in the step (3), the secondary reverse osmosis system is formed by sequentially connecting a precision filter and a secondary reverse osmosis membrane;

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the secondary reverse osmosis membrane is a seawater reverse osmosis membrane;

preferably, the rejection rate of the secondary reverse osmosis membrane on heavy metal ions and salts is more than 99.5%;

preferably, the aperture of the secondary reverse osmosis membrane is 0.1-1 nm;

preferably, the membrane inlet pressure of the secondary reverse osmosis system is 4-5 Mpa;

preferably, the pH of the water entering the secondary reverse osmosis system is 6 to 8;

preferably, the secondary reverse osmosis system is adjusted in pH by adding hydrochloric acid;

preferably, the concentration of the hydrochloric acid is 0.2-0.5%;

preferably, the permeate of the secondary reverse osmosis system returns to the primary nanofiltration system;

preferably, the concentrate of the secondary reverse osmosis system is the high salinity concentrate.

Preferably, in the step (4), the evaporative crystallization treatment step is: sequentially passing the high-salinity concentrated water obtained in the step (3) through a heat exchanger, a concentration evaporator and an evaporation crystallizer;

preferably, the operating temperature of the heat exchanger is 80-100 ℃;

preferably, the operating pressure of the heat exchanger is 0.05-0.1 MPa;

preferably, the concentration evaporator is formed by sequentially connecting a heating chamber, a separation chamber, a circulating chamber, a liquid distributor and a demister;

preferably, the evaporative crystallizer is formed by sequentially connecting a separation chamber, a salt leg, a thickener and a crystallization kettle;

preferably, the condensed water of the high-salinity concentrated water after passing through the concentration evaporator returns to the secondary reverse osmosis system;

preferably, the concentrated high-salt water passes through a concentration evaporator to obtain concentrated high-salt water;

preferably, the concentrated high-salinity concentrated water has the salinity of 30-35%;

preferably, the concentrated high-salinity concentrated water passes through an evaporative crystallizer to obtain a crystal substance and condensed water; preferably, the crystal is sodium sulfate and/or sodium chloride; preferably, the condensed water is used as reuse water.

The invention also provides a treatment system of the zinc-containing wastewater treatment method, which is characterized by comprising a pretreatment unit, a biochemical treatment unit, a concentration treatment unit and an evaporation crystallization treatment unit which are sequentially communicated.

Preferably, the pretreatment unit comprises a zinc breaking tank, a pH adjusting tank, a chemical reaction tank and a precise control efficient precipitation system which are sequentially communicated; the precise control efficient sedimentation system is formed by sequentially connecting a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge bucket.

Preferably, the biochemical treatment unit comprises an anaerobic tank, an aerobic tank and a membrane bioreactor which are communicated in sequence;

preferably, the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool;

preferably, the hollow fiber membrane module is located in the membrane tank;

preferably, the pore diameter of the hollow fiber membrane is 0.01-0.1 μm.

Preferably, the concentration treatment unit comprises a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system which are communicated in sequence.

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the filter element pore size of the precision filter is 5 μm;

the primary nanofiltration membrane is an industrial grade high-desalination-rate nanofiltration membrane;

preferably, the aperture of the primary nanofiltration membrane is 1-2 nm;

preferably, the rejection rate of the primary nanofiltration membrane to sodium ions is 50-70%; preferably, the rejection rate of the primary nanofiltration membrane on heavy metal ions and salts is more than 97%;

preferably, the pH of the water entering the primary nanofiltration system is 6-8.

Preferably, the first-stage reverse osmosis system is formed by sequentially connecting a precision filter and a first-stage reverse osmosis membrane;

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the filter element pore size of the precision filter is 5 μm;

preferably, the aperture of the primary reverse osmosis membrane is 0.1-1 nm;

preferably, the concentration of the hydrochloric acid is 0.2-0.5%.

Preferably, the secondary reverse osmosis system is formed by sequentially connecting a precision filter and a secondary reverse osmosis membrane;

preferably, the filter element of the precision filter is melt-blown PP cotton;

preferably, the filter element pore size of the precision filter is 5 μm;

preferably, the aperture of the secondary reverse osmosis membrane is 0.1-1 nm;

preferably, the concentration of the hydrochloric acid is 0.2-0.5%.

Preferably, the evaporative crystallization unit comprises a heat exchanger, a concentration evaporator and an evaporative crystallizer which are communicated in sequence;

preferably, the operating temperature of the heat exchanger is 80-100 ℃;

preferably, the operating pressure of the heat exchanger is 0.05-0.1 MPa;

preferably, the evaporative crystallizer consists of a separation chamber, a salt leg, a thickener and a crystallization kettle which are connected in sequence.

The treatment method of the zinc-containing wastewater or the treatment system of the zinc-containing wastewater treatment method is applied to the treatment of the zinc-containing wastewater.

In order to overcome the defects in the zinc-containing wastewater treatment in the prior art, the provided zinc-containing wastewater treatment method comprises the following steps:

the invention discloses a method for analyzing the pollutant source of zinc-containing wastewater, which comprises the following steps: the zinc-containing wastewater is mainly wastewater generated in the working procedures of cleaning a plated part, cleaning a polar plate, passivating zinc and other plated parts, electrolytic polishing of stainless steel, anodizing of aluminum, treating the plated part and the like after an electroplating process, has pH of 6-8, and contains pollutants such as zinc, SS, COD and the like;

the zinc-containing wastewater treatment method and the zinc-containing wastewater treatment system provided by the invention have the advantages that through the technical route of wastewater diversion, classification treatment, wastewater recycling and resource recovery, the electroplating heavy metal zinc-containing wastewater is completely recycled for production after being treated by adopting a heavy metal high-precision removal technology, a high-salinity wastewater biochemical technology, a special membrane concentration technology and a mechanical negative pressure evaporation crystallization technology, the zero discharge of the wastewater is realized, the wastewater reuse rate is improved to 99.67%, the cyclic utilization of water resources is realized to the maximum extent, pollutants in the wastewater are converted into solids for recycling, and the zero discharge of the wastewater is thoroughly realized.

The zinc-containing wastewater pretreatment process comprises the following steps: 1. introducing the zinc-containing wastewater into a zinc breaking tank, adding sulfuric acid into the zinc breaking tank to reach the pH value of 2-3, then adding sodium hypochlorite to reach the ORP value of 300-400mv, then introducing the wastewater into a pH adjusting tank, and adding sodium hydroxide to reach the pH value of 8.5-9.5; 2. introducing the wastewater into a chemical reaction tank, adding a coagulant and then adding a flocculant for stirring for 20-30min to form larger alum flocs (0.6-1.0mm) in order to accelerate coagulation reaction, thereby accelerating precipitation, realizing that the coagulant and the flocculant are added at different time intervals in the flocculation process to ensure that the coagulant and the flocculant are in the best reaction time, adopting mechanical stirring in a flocculation reaction system, having high reaction speed, good effect and less dosage, and having higher removal effect on phosphorus, fluorine and COD while removing heavy metals; 3. then introducing a precise control efficient precipitation system; the precise control efficient sedimentation system is formed by sequentially connecting a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge hopper; introducing the treated wastewater into the water distribution system, the sedimentation treatment tank and the inclined pipe in sequence; the supernatant after the treatment enters an effluent weir to obtain pretreated water, and sludge is deposited in a sludge hopper; in order to increase the precipitation area, shorten the precipitation time and improve the precipitation efficiency, the precise control efficient precipitation system efficiently precipitates flocs and SS under the action of hydraulic water distribution, efficient precipitation and the like, the inclined pipe is arranged in the tank at the same time, so that the precipitated particles are not interfered by steady flow, and the rapid precipitation effect is achieved, the processing capacity of the precise control efficient precipitation system is 3-7 times greater than that of a common precipitation tank, the sludge at the bottom of the tank is discharged into a sludge tank through a static pressure sludge discharge device for further concentration, and then is pumped into a sludge filter press for filter pressing, and sludge cakes are reprocessed according to properties, so that about 80% of suspended matters and 40-70% of oils can be removed, the turbidity of the effluent is less than 30NTU, the COD is reduced by 40-60%, and the like;

the invention relates to a zinc-containing wastewater biochemical treatment process which comprises the following steps: the pretreated water sequentially enters an anaerobic tank, an aerobic tank and a membrane bioreactor; removing most of COD, ammonia nitrogen, SS and other substances in the wastewater through biodegradation of the A/O/MBR; the anaerobic process of the invention utilizes the function of anaerobic bacteria under the condition of no dissolved oxygen or under the condition of oxygen deficiency to hydrolyze and acidify organic matters, remove the organic matters in the wastewater, improve the biodegradability of the sewage and be beneficial to the subsequent aerobic treatment process; the aerobic process is that under aerobic condition, organic matter is oxidized and decomposed under the action of aerobic microbe, the concentration of organic matter is reduced, the amount of microbe is increased, the organic matter in sewage is adsorbed on the surface of active sludge and biomembrane and contacts with the surface of microbe cell, small molecular organic matter can enter microbe body through cell wall directly, and large molecular organic matter must be hydrolyzed into small molecular under the action of extracellular enzyme-hydrolase and then taken into cell body by microbe. The organic matter is finally decomposed into CO₂And H₂O; the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool; preferably, the hollow fiber membrane module is located in the membrane tank; the membrane component is placed in the membrane pool, aeration is carried out in the pool, and as the aperture of the hollow fiber membrane is smaller than 0.1 micron, zoogloea and free bacteria can be completely retained in the membrane pool, so that mud-water separation is achieved, various suspended particles, bacteria, algae, turbidity and organic matters are effectively removed, and excellent effluent quality with the effluent suspended matters close to zero is ensured. The efficient interception function of the membrane bioreactor can effectively intercept nitrifying bacteria, so that the nitrification reaction is smoothly carried out, and ammonia nitrogen is effectively removed; meanwhile, macromolecular organic matters which are difficult to degrade can be intercepted, and the retention time of the macromolecular organic matters in the biochemical reaction tank is prolonged, so that the macromolecular organic matters are decomposed to the maximum extent.

The invention discloses a zinc-containing wastewater concentration treatment process which comprises the following steps: the biochemical treatment water sequentially passes through a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system; in order to realize zero emission of the zinc-containing wastewater, the rear end of the biochemical treatment system is provided with a concentration treatment system for treating strong brine generated by the biochemical treatment system; the concentration treatment system is a process combining multi-stage concentration and nanofiltration/reverse osmosis concentration, and gradually reduces the water amount of the high-salt-content wastewater (the salt content of the obtained high-salt concentrated water is 40-60g/L) through the step-by-step concentration of the membrane, so that the investment and the operating cost of a subsequent evaporative crystallization system are reduced; the concentration treatment process reduces the concentrated brine to be treated in a subsequent evaporation crystallization system by 80 percent compared with a conventional concentration treatment system, reduces the investment cost of the whole wastewater treatment system by 20 to 30 percent, reduces the running cost of wastewater treatment by 30 to 40 percent, and improves the automation degree of the system.

The invention discloses an evaporative crystallization treatment process of zinc-containing wastewater, which comprises the following steps: the high-salinity concentrated water obtained by concentration treatment sequentially passes through a heat exchanger, a concentration evaporator and an evaporation crystallizer; the wastewater is treated to the evaporation crystallization stage and then is completely recycled, so that zero discharge of the zinc-containing wastewater is realized; the waste water firstly enters a heat exchanger in the evaporative crystallization system, and the O in the waste water is removed through heat exchange₂And CO₂And (3) gas and waste water after heat exchange enter a concentration evaporator for evaporation concentration, when the salt concentration of the waste water is 30-35%, namely before sodium sulfate and sodium chloride are crystallized, the waste water is sent to an evaporation crystallizer to obtain crystals and condensed water, and the condensed water is used as reuse water. The evaporative crystallization system utilizes mechanical temperature increasing equipment to cause negative pressure of the waste water evaporation part, so that energy can be saved, compressed waste water steam is heated and pressurized to enter the outside of a concentration evaporator, latent heat is transferred to a pipe, the pipe is condensed into condensed water, and meanwhile, salt-containing waste water in the pipe is evaporated. The evaporative crystallization system has the characteristics of small volume, small occupied area, low energy consumption and high thermal efficiency, the power consumption of one ton of waste water is 16-20kwh, the thermal efficiency is 27 times that of a single-effect flash evaporation system and 7 times that of a four-effect flash evaporation system, the evaporative crystallization system is the most advanced evaporative concentration system at present, the generated crystals can be treated or sent to related departments for purification and utilization, and the main components of the evaporative crystallization system are sodium sulfate and sodium chloride.

The advantages of the evaporative crystallization system are as follows: (1) the system adopts mixed process water supply to reduce the ton water power consumption of the same water making tonnage device by 40-50% compared with the foreign technology; (2) because the mixed process of the system supplies water, the high-salinity concentrated water passing through the concentration treatment system sequentially enters the low-temperature effect from the high-temperature effect of the evaporative crystallization system, the concentration is gradually increased, and the temperature is gradually reduced. The increase of the concentration of the high-temperature effect feed water caused by circulating feed water from low-temperature effect to high-temperature effect in foreign technologies is avoided, and the scaling and corrosion conditions of high-temperature effect are effectively reduced; (3) the high-salinity concentrated water passing through the concentration treatment system is uniformly distributed on the concentration evaporator, so that the defect that the spray head type water supply in the existing evaporative crystallization system is not uniform and is easy to block is avoided; (4) the vacuum system adopts a differential pressure air extractor, and the designed differential pressure is accurately formed among the effects, so that the system is stable and reliable in operation.

The treatment system of the zinc-containing wastewater treatment method adopts the programmable logic controller, simultaneously realizes the automatic control and monitoring of electric instruments, and adopts the industrial personal computer to monitor the operation process state and the operation parameters of the system. In addition, a membrane system in the system is periodically flushed by using a permeate liquid to flush pollutants and protect a membrane; and an on-line chemical cleaning system is established, so that long-term, stable and efficient operation of the system can be ensured.

At present, the conventional treatment technology of the zinc-containing wastewater in the prior art comprises a chemical precipitation technology, a biological treatment technology and a membrane separation technology, the conventional technology is mainly designed according to a route of standard discharge, and compared with the invention, the invention has the following defects:

(1) the system waste water reuse rate of the conventional technology is 60%, wherein water resources are not fully recycled, and the waste water is discharged after being treated, so that the load of the surrounding environment is increased;

(2) the tolerance of the microorganism to salt in the conventional biochemical treatment technology is poor, the sludge concentration is generally 3000mg/L, and the sludge concentration of the biochemical system in the technology of the invention is 7000-8000 mg/L.

(3) Heavy metal ions are not removed 100%, and environmental pollution still exists;

(4) concentrated water generated by the membrane concentration system needs to be treated again, otherwise, two layers of pollution can be caused;

(5) the conductivity of the reuse water in the conventional technology is 200-300 mu S/cm, and the conductivity of the reuse water in the technology is less than or equal to 50 mu S/cm.

The zinc-containing wastewater treatment method and the zinc-containing wastewater treatment system have the beneficial effects that:

(1) according to different reaction conditions of various heavy metal ions, the zinc-containing wastewater pretreatment process adopts online monitoring instruments such as pH and ORP, automatically controls a metering pump to quantitatively feed chemicals, adds the chemicals to fully react with the wastewater, and carries out solid-liquid separation treatment through a precisely controlled high-efficiency precipitation system, so that the removal rate of the heavy metal ions can reach 99.99%.

(2) The biochemical process of the zinc-containing wastewater adopts an A/O/MBR process, the system consists of a biochemical tank, a membrane component and a membrane tank, and can completely retain activated sludge in the membrane tank, so that various suspended particles, bacteria, organic matters and other pollutants stay for a long time, are fully removed, the quality of effluent is ensured to be excellent, and SS is almost zero. The process has high volume load and strong adaptability to water quality and water quantity, and adopts the domesticated special microorganism with salt tolerance to remove the wastewater with high salt content and hard-to-degrade COD with high efficiency and good denitrification effect.

(3) The zinc-containing wastewater concentration process adopts a special membrane concentration technology to concentrate the salt in the wastewater by more than 30 times according to the technology of combining desalination concentration and fine desalination concentration, and the produced water of an advanced treatment system can be directly reused for production. The special membrane concentration technology has the characteristics of high efficiency desalination rate under high flow rate, higher mechanical strength, longer service life, capability of playing a function under lower operation pressure, good chemical stability and high cost performance.

(4) The evaporation crystallization of the zinc-containing wastewater adopts a German special vapor compression technology and comprises a distilled water heat exchanger, a concentration evaporator, a crystallizer, a centrifuge and the like, when the evaporator is used for treating the wastewater, the heat energy required by the evaporation of the wastewater is provided by the heat energy released when the steam is condensed and the condensed water is cooled, and no latent heat is lost in the operation process, so that the wastewater is evaporated at low temperature and negative pressure. When the compressor compresses, the pressure and the temperature are increased, and the high enthalpy steam is used as a heat source again to fully recover the heat of the distilled water and the concentrated solution, thereby saving the energy consumption. During evaporation, the evaporation outside the pipe is adopted, so that the efficiency is high and the scale in the pipe is never accumulated.

Drawings

Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 is a schematic view of a zinc-containing wastewater treatment system according to the present invention.

Detailed Description

The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.

The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials and reagent materials used in the following examples are all commercially available products unless otherwise specified.

the zinc-containing wastewater pretreatment process comprises the following steps: 1. introducing the zinc-containing wastewater into a zinc breaking tank, adding sulfuric acid into the zinc breaking tank to reach pH, then adding sodium hypochlorite until the ORP value is 300-400mv, then introducing the wastewater into a pH adjusting tank, and adding sodium hydroxide until the pH value is 8.5-9.5; 2. introducing the wastewater into a chemical reaction tank, adding a coagulant and then adding a flocculant for stirring for 20-30min to form larger alum flocs (0.6-1.0mm) in order to accelerate coagulation reaction, thereby accelerating precipitation, realizing that the coagulant and the flocculant are added at different time intervals in the flocculation process to ensure that the coagulant and the flocculant are in the best reaction time, adopting mechanical stirring in a flocculation reaction system, having high reaction speed, good effect and less dosage, and having higher removal effect on phosphorus, fluorine and COD while removing heavy metals; 3. then introducing a precise control efficient precipitation system; preferably, the precise control efficient sedimentation system is formed by sequentially connecting a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge hopper; introducing the treated wastewater into the water distribution system, the sedimentation treatment tank and the inclined pipe in sequence; the supernatant after the treatment enters an effluent weir to obtain pretreated water, and sludge is deposited in a sludge hopper; in order to increase the precipitation area, shorten the precipitation time and improve the precipitation efficiency, the precise control efficient precipitation system efficiently precipitates flocs and SS under the action of hydraulic water distribution, efficient precipitation and the like, the inclined pipe is arranged in the tank at the same time, so that the precipitated particles are not interfered by steady flow, and the rapid precipitation effect is achieved, the processing capacity of the precise control efficient precipitation system is 3-7 times greater than that of a common precipitation tank, the sludge at the bottom of the tank is discharged into a sludge tank through a static pressure sludge discharge device for further concentration, and then is pumped into a sludge filter press for filter pressing, and sludge cakes are reprocessed according to properties, so that about 80% of suspended matters and 40-70% of oils can be removed, the turbidity of the effluent is less than 30NTU, the COD is reduced by 40-60%, and the like;

the invention relates to a zinc-containing wastewater biochemical treatment process which comprises the following steps: the pretreated water sequentially enters an anaerobic tank, an aerobic tank and a membrane bioreactor; removing most of COD, ammonia nitrogen, SS and other substances in the wastewater through biodegradation of the A/O/MBR; the anaerobic process of the invention utilizes the function of anaerobic bacteria under the condition of no dissolved oxygen or under the condition of oxygen deficiency to hydrolyze and acidify organic matters, remove the organic matters in the wastewater, improve the biodegradability of the sewage and be beneficial to the subsequent aerobic treatment process; the aerobic process is that under aerobic condition, organic matter is oxidized and decomposed under the action of aerobic microbe, the concentration of organic matter is reduced, the amount of microbe is increased, the organic matter in sewage is adsorbed on the surface of active sludge and biomembrane and contacts with the surface of microbe cell, small molecular organic matter can enter microbe body through cell wall directly, and large molecular organic matter must be hydrolyzed into small molecular under the action of extracellular enzyme-hydrolase and then taken into cell body by microbe. The organic matter is finally decomposed into CO₂And H₂O; the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool; preferably, the hollow fiber membrane module is located in the membrane tank; the membrane component is placed in the membrane tank, aeration is carried out in the membrane tank, and bacteria can be cultured due to the fact that the aperture of the hollow fiber membrane is smaller than 0.1 micrometerThe micelle and the free bacteria are all kept in the membrane tank, so that mud and water separation is achieved, various suspended particles, bacteria, algae, turbidity and organic matters are effectively removed, and the excellent effluent quality with the effluent suspended matters close to zero is ensured. The efficient interception function of the membrane bioreactor can effectively intercept nitrifying bacteria, so that the nitrification reaction is smoothly carried out, and ammonia nitrogen is effectively removed; meanwhile, macromolecular organic matters which are difficult to degrade can be intercepted, and the retention time of the macromolecular organic matters in the biochemical reaction tank is prolonged, so that the macromolecular organic matters are decomposed to the maximum extent.

The invention discloses an evaporative crystallization treatment process of zinc-containing wastewater, which comprises the following steps: the high-salinity concentrated water obtained by concentration treatment sequentially passes through a heat exchanger, a concentration evaporator and an evaporation crystallizer; the wastewater is treated to the evaporation crystallization stage and then is completely recycled, so that zero discharge of the zinc-containing wastewater is realized; the waste water firstly enters a heat exchanger in the evaporative crystallization system, and the O in the waste water is removed through heat exchange₂And CO₂And (3) gas and waste water after heat exchange enter a concentration evaporator for evaporation concentration, when the salt concentration of the waste water is 30-35%, namely before sodium sulfate and sodium chloride are crystallized, the waste water is sent to an evaporation crystallizer to obtain crystals and condensed water, and the condensed water is used as reuse water. The evaporative crystallization system of the present inventionThe system utilizes mechanical heating equipment to cause the negative pressure of the waste water evaporation part, can save energy, and the compressed waste water steam is heated and pressurized to enter the outside of the concentration evaporator, and latent heat is transferred to the pipe, and the latent heat is condensed into condensed water, and meanwhile, the salt-containing waste water in the pipe is evaporated. The evaporative crystallization system has the characteristics of small volume, small occupied area, low energy consumption and high thermal efficiency, the power consumption of one ton of waste water is 16-20kwh, the thermal efficiency is 27 times that of a single-effect flash evaporation system and 7 times that of a four-effect flash evaporation system, the evaporative crystallization system is the most advanced evaporative concentration system at present, the generated crystals can be treated or sent to related departments for purification and utilization, and the main components of the evaporative crystallization system are sodium sulfate and sodium chloride.

The process flow of the following embodiment of the invention comprises the following basic treatment flows: electroplating zinc-containing wastewater → pretreatment process → biochemical treatment process → anaerobic tank → aerobic tank → membrane bioreactor → pressurization → first-stage nanofiltration membrane separation → pressurization → first-stage reverse osmosis membrane separation → pressurization → second-stage reverse osmosis membrane separation, and high-salinity concentrated water enters an evaporative crystallization system after separation; in the evaporative crystallization system, condensed water generated by treating high-salinity concentrated water by a concentration evaporator can meet the water quality requirement of workshop reuse water.

Example 1

(1) Pretreating zinc-containing wastewater to obtain pretreated water

Firstly, taking zinc-containing wastewater, wherein the zinc-containing wastewater is mainly wastewater generated in the working procedures of cleaning a plated part, cleaning a polar plate, passivating the plated part such as zinc and the like, electrolytic polishing of stainless steel, anodizing aluminum, treating the plated part and the like after an electroplating process, and has the pH of 6-8 and contains pollutants such as zinc, SS, COD and the like;

introducing the zinc-containing wastewater into a zinc breaking tank, adding a 10% sulfuric acid solution into the zinc breaking tank until the pH value is 2-3, then adding a 10% sodium hypochlorite solution until the ORP value is 300-400mv, and carrying out zinc breaking reaction; then introducing the wastewater into a pH adjusting tank, adding a 10% sodium hydroxide solution, adjusting the pH to 8.5-9.5, introducing the wastewater into a chemical reaction tank, adding a coagulant PAC and a flocculant PAM, and stirring for 25 min. And then introducing the wastewater into a precise control efficient precipitation system.

(2) Performing biochemical treatment on the pretreated water to obtain biochemical treated water

The pretreated water sequentially enters an anaerobic tank, an aerobic tank and a membrane bioreactor; wherein the anaerobic pool contains anaerobic bacteria, and the anaerobic bacteria are selected from one or more of yeast, nitrate bacteria, clostridium or bacteroides; the yeast, nitrate bacteria, clostridium or bacteroides are domesticated to have salt tolerance; wherein the aerobic tank contains aerobic microorganisms, and the aerobic microorganisms are selected from one or more of bacillus, rhizobium, nitrobacteria or mould; the bacillus, the rhizobium, the nitrobacteria or the mould is domesticated to enable the bacillus, the rhizobium, the nitrobacteria or the mould to have salt tolerance; then enters a membrane bioreactor which consists of a hollow fiber membrane (the aperture of the hollow fiber membrane is 0.01-0.1 mu m) component and a membrane pool; the membrane assembly is placed in a membrane tank, aeration is carried out in the membrane tank, the pH value after biochemical treatment is 6-8, and most of substances such as COD, ammonia nitrogen, SS and the like in the wastewater can be removed; the anaerobic process of the invention utilizes the function of anaerobic bacteria under the condition of no dissolved oxygen or under the condition of oxygen deficiency to hydrolyze and acidify organic matters, remove the organic matters in the wastewater, improve the biodegradability of the sewage and be beneficial to the subsequent aerobic treatment process; the aerobic process is that under aerobic condition, organic matter is oxidized and decomposed under the action of aerobic microbe, the concentration of organic matter is reduced, the amount of microbe is increased, the organic matter in sewage is adsorbed on the surface of active sludge and biomembrane and contacts with the surface of microbe cell, small molecular organic matter can enter microbe body through cell wall directly, and large molecular organic matter must be hydrolyzed into small molecular under the action of extracellular enzyme-hydrolase and then taken into cell body by microbe. The organic matter is finally decomposed into CO₂And H₂O; the membrane bioreactor comprises a hollow fiber membrane component and a membrane pool, wherein the membrane component is placed in the membrane pool, aeration is carried out in the membrane pool, and as the pore diameter of the hollow fiber membrane is smaller than 0.1 micron, zoogloea and free bacteria can be completely retained in the membrane pool, so that mud-water separation is achieved, various suspended particles, bacteria, algae, turbidity and organic matters are effectively removed, and the excellent effluent quality with the effluent suspended matters close to zero is ensured. Membrane organismsThe efficient interception function of the reactor can effectively intercept nitrifying bacteria, so that the nitrification reaction is smoothly carried out, and ammonia nitrogen is effectively removed; meanwhile, macromolecular organic matters which are difficult to degrade can be intercepted, and the retention time of the macromolecular organic matters in the biochemical reaction tank is prolonged, so that the macromolecular organic matters are decomposed to the maximum extent.

(3) Concentrating the biochemical treatment water to obtain high-salinity concentrated water and reuse water

The biochemical treatment water sequentially passes through a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system; the primary nanofiltration system is formed by sequentially connecting a precision filter and a primary nanofiltration membrane, wherein a filter element of the precision filter is melt-blown PP cotton, the aperture of the precision microporous filter is 5 mu m, the aperture of the primary nanofiltration membrane is 1nm, when water to be treated passes through the primary nanofiltration membrane, the rejection rate of sodium ions is 50%, and the rejection rate of heavy metal ions and salt is 98%; then passing through a primary nanofiltration system, wherein the pH is 6-8, and the membrane inlet pressure is 1.5 Mpa; the relative molecular mass interception range of the primary nanofiltration system is 300 daltons; the permeate of the primary nanofiltration system can be used as reuse water for continuous use through ion exchange;

the concentrated solution of the treated water passing through the primary nanofiltration system enters a primary reverse osmosis system, the primary reverse osmosis system is formed by sequentially connecting a precision filter and a primary reverse osmosis membrane (a brackish water reverse osmosis membrane with the aperture of 0.1-1nm), the membrane inlet pressure of the primary reverse osmosis system is 1.8Mpa, the pH is adjusted to 5-6 by 0.2% hydrochloric acid, and the rejection rate of heavy metal ions and salt is 99% by the primary reverse osmosis membrane; the permeate of the treated water passing through the primary reverse osmosis system returns to the primary nanofiltration system, and the concentrated solution enters the secondary reverse osmosis system. The secondary reverse osmosis system is formed by sequentially connecting a precision filter and a secondary reverse osmosis membrane (a seawater reverse osmosis membrane with the aperture of 0.1-1 nm); the membrane inlet pressure of the secondary reverse osmosis system is 5Mpa, the pH value is adjusted to 6-8 by 0.2% hydrochloric acid, and the rejection rate of heavy metal ions and salt is 99.9% by the secondary reverse osmosis membrane; and the permeate of the treated water passing through the secondary reverse osmosis system returns to the primary nanofiltration system, the concentrated solution is high-salt concentrated water, and the salt content of the high-salt concentrated water is 40 g/L.

In order to realize zero emission of the zinc-containing wastewater, the rear end of the biochemical treatment system is provided with a concentration treatment system for treating strong brine generated by the biochemical treatment system; the concentration treatment system is a process combining multi-stage concentration and nanofiltration/reverse osmosis concentration, and gradually reduces the water amount of the high-salt-content wastewater (the salt content of the obtained high-salt concentrated water is 40g/L) through the step-by-step concentration of the membrane, so that the investment and the operating cost of a subsequent evaporative crystallization system are reduced; the concentration treatment process reduces the concentrated brine to be treated in a subsequent evaporation crystallization system by 80 percent compared with a conventional concentration treatment system, reduces the investment cost of the whole wastewater treatment system by 30 percent, reduces the running cost of wastewater treatment by 40 percent, and improves the automation degree of the system. The zinc-containing wastewater concentration treatment process comprises the steps of pre-concentrating by a precision filter and a primary nanofiltration system, performing ion exchange on permeate of the primary nanofiltration system to obtain reuse water, and enabling concentrated solution of the primary nanofiltration system to enter a primary reverse osmosis system; the permeate of the primary reverse osmosis system returns to the primary nanofiltration system, and the concentrated solution of the primary reverse osmosis system enters the secondary reverse osmosis system; and the permeate of the secondary reverse osmosis system returns to the primary nanofiltration system, and the concentrated solution of the secondary reverse osmosis system is the high-salinity concentrated water.

(4) Carrying out evaporation crystallization treatment on the high-salinity concentrated water to obtain recycled water and crystals

Sequentially passing the high-salinity concentrated water through a heat exchanger, a concentration evaporator and an evaporation crystallizer; the operating temperature of the heat exchanger is 80-100 ℃; the operating pressure of the heat exchanger is 0.05-0.1 MPa; the concentration evaporator is formed by sequentially connecting a heating chamber, a separation chamber, a circulating chamber, a liquid distributor and a demister; the evaporative crystallizer is formed by sequentially connecting a separation chamber, salt legs, a thickener and a crystallization kettle; the condensed water of the high-salinity concentrated water after passing through the concentration evaporator returns to the secondary reverse osmosis system; the concentrated solution obtained after the high-salt concentrated water passes through a concentration evaporator is concentrated high-salt concentrated water, and the salt content is 40-60 g/L; the concentrated high-salinity concentrated water passes through an evaporative crystallizer to obtain a crystal and condensed water; the obtained crystal is sodium sulfate and/or sodium chloride; and the condensed water is returned to the workshop as reuse water for continuous use.

Wherein, the concentration evaporator is composed of a plurality of evaporators connected in series, low-temperature (about 90 ℃) heating steam is introduced into the first effect to heat feed liquid therein, so that the feed liquid generates almost equivalent evaporation with the temperature lower than that of the steam. The steam produced is introduced into the second effect as heating steam, causing the feed liquid of the second effect to evaporate at a lower temperature than the first effect. This process is repeated until the final effect. The first effect condensate water returns to the heat source, other effect condensate water is collected and then output as desalted water, and one part of steam is input and can evaporate multiple times of water to be output. Meanwhile, the feed liquid is sequentially concentrated from the first effect to the last effect, and the feed liquid is supersaturated at the last effect and crystallized and separated out. Thereby realizing the solid-liquid separation of the feed liquid.

The technical parameters of the evaporative crystallization system for treating concentrated water are as follows:

(1) the desalted water has a salt content (TDS) of less than 10ppm

(2) Consumption of steam for desalting per ton is (1/effect number)/90% t/t

(3) The electric power consumption of the desalinated water is 2-4 kwh/t

Compared with the prior art, the zinc-containing wastewater treatment method disclosed by the invention not only improves the wastewater reuse rate to 99.67%, but also can greatly reduce the treatment cost, reduce the solid waste production and the metal ion resource in the wastewater, and thoroughly realize zero discharge of the wastewater.

Comparative example 1

(1) Firstly, taking zinc-containing wastewater, wherein the zinc-containing wastewater is mainly wastewater generated in the working procedures of cleaning a plated part, cleaning a polar plate, passivating the plated part such as zinc and the like, electrolytic polishing of stainless steel, anodizing aluminum, treating the plated part and the like after an electroplating process, and has the pH of 6-8 and contains pollutants such as zinc, SS, COD and the like; introducing the zinc-containing wastewater into a pH adjusting tank, adding sodium hydroxide to adjust the pH to 10-11, and reacting for 20-25 min; and introducing the wastewater into a chemical reaction tank, adding a coagulant PAC and a flocculant PAM, and stirring for 25 min. And introducing the wastewater into a precipitation system for mud-water separation, introducing the sludge into a sludge treatment system, and introducing the supernatant into a biochemical system.

(2) The pretreated water sequentially enters an anaerobic tank, an aerobic tank and a biochemical sedimentation tank; wherein, the anaerobic pool contains anaerobic bacteria, and the aerobic pool contains aerobic microorganisms; then enters a biochemical sedimentation tank, and the biochemical sedimentation tank consists of a water distribution area, a sludge area, a separation area and a water outlet weir; the SS of the effluent of the biochemical sedimentation tank is 30mg/L, the COD is 50mg/L, 40 percent of the effluent of the biochemical sedimentation tank reaches the standard and is discharged, and 60 percent of the effluent enters a membrane concentration system.

(3) The effluent after biochemical treatment sequentially passes through a precision filter and a reverse osmosis membrane device; wherein the filter element of the precise filter is PP cotton, and the aperture of the precise microporous filter is 5 mu m; the membrane inlet pressure of the reverse osmosis system is 1.2-1.6Mpa, the pH value is adjusted to 5-6 by hydrochloric acid, and the rejection rate of heavy metal ions and salt is 99% by the reverse osmosis membrane; the concentrated solution of the reverse osmosis membrane returns to the pretreatment system for treatment, the conductivity of the permeate of the reverse osmosis membrane is 200 and 300 mu S/cm, which accounts for about 60 percent of the total wastewater, and the permeate is recycled to the production line as reuse water.

In conclusion, the above description of the embodiments of the present invention is not intended to limit the present invention, and those skilled in the art can make various changes or modifications according to the present invention without departing from the spirit of the present invention, which falls within the scope of the appended claims.

Claims

1. A zinc-containing wastewater treatment method is characterized in that the treatment method comprises the following steps in sequence:

(1) pretreating zinc-containing wastewater to obtain pretreated water;

wherein, in the step (1), the step of preprocessing is:

(1-4) introducing the wastewater treated in the step (1-3) into a precise control efficient precipitation system; the precise control efficient sedimentation system comprises a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge hopper;

in the step (2), the biochemical treatment step is as follows: sequentially feeding the pretreated water obtained in the step (1) into an anaerobic tank, an aerobic tank and a membrane bioreactor; the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool, wherein the hollow fiber membrane component is positioned in the membrane pool, and the aperture of the hollow fiber membrane is 0.01-0.1 mu m;

in the step (3), the concentration treatment step is: sequentially passing the biochemical treatment water obtained in the step (2) through a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system;

the primary nanofiltration system is formed by sequentially connecting a precision filter and a primary nanofiltration membrane; the filter element of the precision filter is melt-blown PP cotton; the primary nanofiltration membrane is an industrial grade high-desalination-rate nanofiltration membrane; the aperture of the filter element of the precision filter is 5 mu m; the aperture of the primary nanofiltration membrane is 1-2nm, and the membrane inlet pressure of the primary nanofiltration system is 1.0-1.5 Mpa; the permeate of the primary nanofiltration system is used as reuse water; the concentrated solution of the primary nanofiltration system enters a primary reverse osmosis system;

the first-stage reverse osmosis system is formed by sequentially connecting a precision filter and a first-stage reverse osmosis membrane; wherein the filter element of the precision filter is melt-blown PP cotton; the first-stage reverse osmosis membrane is a brackish water reverse osmosis membrane, the aperture of a filter element of the precision filter is 5 mu m, and the aperture of the first-stage reverse osmosis membrane is 0.1-1 nm; the membrane inlet pressure of the primary reverse osmosis system is 1.8Mpa, and the permeate of the primary reverse osmosis system returns to the primary nanofiltration system; the concentrated solution of the first-stage reverse osmosis system enters a second-stage reverse osmosis system;

the secondary reverse osmosis system is formed by sequentially connecting a precision filter and a secondary reverse osmosis membrane; the filter element of the precision filter is melt-blown PP cotton; the secondary reverse osmosis membrane is a seawater reverse osmosis membrane, the aperture of a filter element of the precision filter is 5 mu m, the aperture of the secondary reverse osmosis membrane is 0.1-1nm, the membrane inlet pressure of the secondary reverse osmosis system is 4-5Mpa, and the permeate of the secondary reverse osmosis system returns to the primary nanofiltration system; the concentrated solution of the secondary reverse osmosis system is the high-salinity concentrated water;

in the step (4), the evaporation crystallization treatment step is as follows: sequentially passing the high-salinity concentrated water obtained in the step (3) through a heat exchanger, a concentration evaporator and an evaporation crystallizer; the operating temperature of the heat exchanger is 80-100 ℃; the operating pressure of the heat exchanger is 0.05-0.1 MPa;

condensed water obtained after the high-salinity concentrated water passes through a concentration evaporator returns to the secondary reverse osmosis system; the high-salinity concentrated water passes through a concentration evaporator to obtain concentrated high-salinity concentrated water; the concentrated high-salinity concentrated water passes through an evaporative crystallizer to obtain a crystal and condensed water; the crystal is sodium sulfate and/or sodium chloride; the condensed water is used as reuse water;

wherein the standard of the recycled water is as follows: pH is 6-8, conductivity is less than or equal to 50 mu S/cm, COD is less than or equal to 30mg/L, and turbidity is less than or equal to 1 NTU.

2. The treatment method according to claim 1, wherein in the step (1), the zinc-containing wastewater has pH 6-8 and contains zinc ions, SS and COD pollutants; wherein Zn in the zinc-containing wastewater²⁺Is 30-50 mg/L.

3. The treatment method according to claim 1, wherein in the step (1), in the step (1-1), a sulfuric acid solution with a concentration of 10% is added to adjust the pH; adding sodium hypochlorite solution with the concentration of 10% to adjust the ORP value.

4. The treatment method according to claim 1, wherein in the step (1), the zinc breaking reaction time of the step (1-1) is 20-30 min.

5. The treatment method according to claim 1, wherein in the step (1), the pH is adjusted by adding a 10% sodium hydroxide solution in the step (1-2).

6. The process according to claim 1, wherein in the step (1), the coagulant is PAC in the steps (1-3); the flocculant is PAM; the time interval between the coagulant and the flocculant is 20-40 min.

7. The treatment method according to claim 1, wherein the wastewater treated in the step (1-3) is introduced into the water distribution system, the sedimentation treatment tank and the inclined pipe in sequence; the supernatant after the treatment enters an effluent weir to obtain pretreated water, and the obtained sludge is deposited in a sludge hopper; wherein the pressure of the sedimentation treatment tank is 2-3 Mpa.

8. The process of claim 1, wherein in step (2), the anaerobic pond contains anaerobic bacteria; the anaerobic bacteria are selected from one or more of yeast, clostridium and bacteroides.

9. The process of claim 8, wherein the yeast, clostridia or bacteroides is acclimatized to be salt tolerant.

10. The treatment method according to claim 1, wherein in the step (2), the aerobic tank contains aerobic microorganisms; the aerobic microorganism is selected from one or more of bacillus, rhizobium, nitrobacteria and mould.

11. The method of claim 10, wherein the bacillus, rhizobium, nitrifier or mold is acclimated to provide salt tolerance.

12. The process according to claim 1, wherein in the step (2), the post-biochemical treatment has a pH of 6 to 8.

13. The treatment method as claimed in claim 1, wherein the rejection rate of the primary nanofiltration membrane on sodium ions is 50-70%; the rejection rate of the first-stage nanofiltration membrane on heavy metal ions and salts is more than 97%.

14. The process as claimed in claim 1, wherein in the step (3), the relative molecular mass cut-off range of the primary nanofiltration system is 150-300 daltons.

15. The process of claim 1 wherein the primary reverse osmosis membrane has a rejection rate of > 98% for heavy metal ions and salts.

16. The process of claim 1 wherein in step (3) the pH of the water entering the primary reverse osmosis system is between 5 and 6.

17. The process of claim 1 wherein in step (3) the primary reverse osmosis system is adjusted to pH by adding 0.2 to 0.5% hydrochloric acid.

18. The process of claim 1 wherein the secondary reverse osmosis membrane has a rejection rate of > 99.5% for heavy metal ions and salts.

19. The process of claim 1 wherein in step (3) the pH of the water entering the secondary reverse osmosis system is from 6 to 8.

20. The process of claim 1 wherein in step (3) the pH is adjusted by adding 0.2 to 0.5% hydrochloric acid to the secondary reverse osmosis system.

21. The process of claim 1, wherein in step (4),

the concentration evaporator comprises a heating chamber, a separation chamber, a circulation chamber, a liquid distributor and a demister; the evaporative crystallizer comprises a separation chamber, salt legs, a thickener and a crystallization kettle; the salt content of the concentrated high-salt concentrated water is 30-35%.

22. A treatment system for implementing the zinc-containing wastewater treatment method according to any one of claims 1 to 21, wherein the system comprises a pretreatment unit, a biochemical treatment unit, a concentration treatment unit and an evaporative crystallization treatment unit which are connected in sequence; wherein the content of the first and second substances,

the pretreatment unit comprises a zinc breaking tank, a pH adjusting tank, a chemical reaction tank and a precise control efficient precipitation system which are sequentially communicated;

the precise control efficient sedimentation system comprises a water distribution system, a sedimentation treatment tank, an inclined pipe, a water outlet weir and a sludge hopper;

the biochemical treatment unit comprises an anaerobic tank, an aerobic tank and a membrane bioreactor which are communicated in sequence; wherein the membrane bioreactor consists of a hollow fiber membrane component and a membrane pool; the hollow fiber membrane module is positioned in the membrane pool; the aperture of the hollow fiber membrane is 0.01-0.1 μm;

the concentration treatment unit comprises a primary nanofiltration system, a primary reverse osmosis system and a secondary reverse osmosis system which are sequentially communicated; the primary nanofiltration system is formed by sequentially connecting a precision filter and a primary nanofiltration membrane; the filter element of the precision filter is melt-blown PP cotton; the primary nanofiltration membrane is an industrial grade high-desalination-rate nanofiltration membrane; the aperture of the filter element of the precision filter is 5 mu m; the aperture of the primary nanofiltration membrane is 1-2 nm;

the first-stage reverse osmosis system is formed by sequentially connecting a precision filter and a first-stage reverse osmosis membrane; the filter element of the precision filter is melt-blown PP cotton; the first-stage reverse osmosis membrane is a brackish water reverse osmosis membrane; the aperture of the filter element of the precision filter is 5 mu m; the aperture of the first-stage reverse osmosis membrane is 0.1-1 nm;

the secondary reverse osmosis system is formed by sequentially connecting a precision filter and a secondary reverse osmosis membrane; the filter element of the precision filter is melt-blown PP cotton; the secondary reverse osmosis membrane is a seawater reverse osmosis membrane; the aperture of the filter element of the precision filter is 5 mu m; the aperture of the secondary reverse osmosis membrane is 0.1-1 nm;

the evaporative crystallization unit comprises a heat exchanger, a concentration evaporator and an evaporative crystallizer which are sequentially communicated.

23. The treatment system of claim 22, wherein the rejection rate of the primary nanofiltration membrane for sodium ions is 50-70%; the rejection rate of the first-stage nanofiltration membrane on heavy metal ions and salts is more than 97%.

24. The treatment system as claimed in claim 22, wherein the relative molecular mass cut-off of the primary nanofiltration system is in the range of 150-300 daltons.

25. The treatment system of claim 22, wherein the pH of the water entering the primary nanofiltration system is between 6 and 8.

26. The treatment system of claim 22, wherein the primary reverse osmosis membrane has a rejection rate of > 98% for heavy metal ions and salts.

27. The treatment system of claim 22 wherein the pH of the water entering the primary reverse osmosis system is between 5 and 6.

28. The treatment system of claim 22 wherein the primary reverse osmosis system is adjusted to pH by adding hydrochloric acid at a concentration of 0.2 to 0.5%.

29. The treatment system of claim 22, wherein the secondary reverse osmosis membrane has a rejection rate of > 99.5% for heavy metal ions and salts.

30. The treatment system of claim 22, wherein the pH of the water entering the secondary reverse osmosis system is between 6 and 8.

31. The treatment system of claim 22 wherein the secondary reverse osmosis system adjusts the pH by adding hydrochloric acid at a concentration of 0.2 to 0.5%.

32. The processing system of claim 22, wherein; wherein the content of the first and second substances,

the concentration evaporator comprises a heating chamber, a separation chamber, a circulation chamber, a liquid distributor and a demister;

the evaporative crystallizer comprises a separation chamber, salt legs, a thickener and a crystallization kettle.

33. Use of the treatment method of any one of claims 1 to 21 or the treatment system of any one of claims 22 to 32 for treating zinc-containing wastewater.