CN108264180B - Zero-emission treatment method and system for high-salt-content wastewater - Google Patents

Zero-emission treatment method and system for high-salt-content wastewater Download PDF

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CN108264180B
CN108264180B CN201810004269.5A CN201810004269A CN108264180B CN 108264180 B CN108264180 B CN 108264180B CN 201810004269 A CN201810004269 A CN 201810004269A CN 108264180 B CN108264180 B CN 108264180B
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wastewater
salt
reverse osmosis
concentrated water
pressure
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CN108264180A (en
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权秋红
张建飞
石维平
元西方
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Bestter Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4698—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities

Abstract

The invention relates to a zero-emission treatment method and a zero-emission treatment system for high-salt-content wastewater, which comprise a pretreatment process, a reduction process and an evaporative crystallization process for high-salt-content concentrated water, wherein the reduction process for the wastewater is to perform preliminary reduction treatment on the pretreated wastewater through a medium-pressure high-pressure reverse osmosis device to form high-pressure reverse osmosis concentrated water, perform deep concentration treatment through a primary and secondary electric driven ion membrane devices and then concentrate the high-salt-content concentrated water into high-salt-content concentrated water, and the reduction process for the wastewater also recovers water produced in the reduction process to a reuse water tank; the first and second stage ion film driving devices include one anode and one cathode set at interval, and several film pairs comprising anode film, cathode film and partition board are regularly arranged between the anode film and the cathode film, the anode film and the cathode film are homogeneous film, the partition board with homogeneous flow state is between the two films, and the power source of the first and second stage ion film driving devices adopts positive and negative polarity automatic switching high frequency DC power source and utilizes digital program to control the power source.

Description

Zero-emission treatment method and system for high-salt-content wastewater
The application has original application number of 201510981729.6 and the name of the invention is: a divisional application of a zero-discharge treatment method of high-salt wastewater.
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a zero-emission treatment method for high-salt-content wastewater.
Background
In recent years, with the rapid development of industries such as petrochemical industry, electric power industry, metallurgy industry, coal chemical industry and the like, the amount of wastewater containing complex components generated in the industrial production process is also increased year by year, and the problem of how to treat and utilize the wastewater containing complex components is widely regarded. Particularly, in water resource deficient areas, how to utilize the part of waste water is realized, zero discharge of the waste water is realized, and the method has important significance for protecting the surrounding environment and natural water body which people rely on to live, further improving the comprehensive utilization efficiency of water resources and relieving the water resource shortage condition.
The waste water zero discharge technology generally adopts reverse osmosis membrane (RO), Electrodialysis (EDR), Ultrafiltration (UF), membrane reactor (MBR) and other technologies to fully recycle the production waste water, and then adopts the technologies of evaporation and the like to recycle the residual high-salt-content waste water. At present, the reverse osmosis membrane treatment technology has gradually become a very important treatment method in the fields of industrial circulating water treatment, sewage and wastewater reuse and the like.
The reverse osmosis membrane method is used for treating wastewater rapidly, but the technology has increasingly prominent problems when treating wastewater with complex components, and the main problems are represented in two aspects: firstly, the desalination rate that reverse osmosis membrane element can reach is above 98%, and salt and impurity more than 98% in the waste water are held back the separation in the dense water that the system produced, and reverse osmosis membrane process can only reach about 75% to the recycle ratio of waste water, still 25% dense water can not utilize, need directly discharge. The high desalination rate of the reverse osmosis membrane element ensures that the part of concentrated water contains a large amount of calcium ions, magnesium ions, heavy metal ions, silicon ions, colloids, organic pollutants and the like, and if the part of concentrated water is directly discharged, the environment is necessarily polluted. The concentrated water is directly evaporated and crystallized by multiple effects, so the consumed steam amount is large, and the treatment cost of the waste water is increased. Secondly, when the salt-containing complex wastewater is subjected to low-pressure, medium-pressure and high-pressure reverse osmosis concentration and is treated by a reverse osmosis device, organic pollutants and saturated inorganic salts are easy to scale on the membrane surface, so that the separation difficulty is increased, the energy consumption is increased, the economy is poor, and the reliability is low.
Aiming at the treatment method of high-salt complex wastewater, the following methods are commonly used at present: firstly, organic substances which are difficult to degrade in the wastewater are subjected to catalytic oxidation by adopting substances with strong oxidizing property, so that the organic substances in the wastewater are effectively degraded, the wastewater after oxidation treatment enters a biochemical device to remove the organic substances, and the organic substances are directly discharged after being precipitated and filtered by a filtering device. However, this method is directed only to organic substances in wastewater, and has no substantial effect of removing inorganic salt components. Secondly, softening the waste water containing calcium and magnesium, then reducing the waste water through a secondary reverse osmosis device to further recover partial water, and directly discharging a small amount of concentrated water generated after reduction. Although the method can reduce the raw water to a certain extent, the concentration of calcium ions, magnesium ions, heavy metal ions, silicon ions, organic matters and the like contained in the reverse osmosis concentrated water is very high, the recovery rate of the common reverse osmosis membrane is not high when the common reverse osmosis membrane is used for secondary reverse osmosis, even the seawater desalination membrane can only be about 50%, and the discharged concentrated water is still large. Thirdly, the evaporation and crystallization device is utilized to treat the high-salt-content concentrated water after the reduction, mixed salt is formed, and zero emission of wastewater is realized. The method has the advantages that the concentrated high-salinity wastewater is treated more thoroughly, the technology is relatively mature, but a large amount of steam is consumed, the formed mixed salt is solid hazardous waste, the treatment cost is high, and the enterprise is difficult to accept. The three treatment methods are comprehensively analyzed, have defects at present and are difficult to be used for industrialization.
Chinese patent (publication No. CN104445788A) discloses a zero-discharge integrated process for treating and recycling high-salt-content wastewater. The process method provided by the patent comprises the steps of firstly carrying out softening pretreatment on high-salt-content wastewater, and then sequentially passing through an activated carbon adsorption and ultrafiltration device to obtain pretreated produced water; nanofiltration soft water and nanofiltration concentrated water are obtained through a nanofiltration device; obtaining reverse osmosis soft water and reverse osmosis concentrated water through a reverse osmosis device; obtaining electrodialysis soft water and electrodialysis concentrated water through an electrodialysis device; and finally, carrying out evaporative crystallization treatment on the electrodialysis concentrated water through an evaporative crystallization device, periodically transporting salt generated by evaporative crystallization, and finally finishing treatment and recycling of the high-salt-content wastewater, wherein the generated water enters a reuse water tank. The treatment method provided by the patent adopts an integrated process of a high-density clarification tank process, a filtration process, a nanofiltration treatment process and a reverse osmosis treatment process, and although the process can meet the requirement of zero emission of wastewater, the method provided by the patent at least has the following defects: (1) the treatment method only aims at the reverse osmosis concentrated water of low-concentration organic matters, and has no obvious treatment effect on high-salinity wastewater containing refractory organic matters; (2) the treated concentrated water is easy to cause scaling and organic matter blockage of membrane elements in the device, and the recovery rate of wastewater is influenced; (3) this patent lacks the further minimizing measure to waste water for the concentrated water volume that gets into the evaporation crystallization device is big, has taken place the phase transition process during the evaporation water volume, and the energy consumption that consumes during the evaporation crystallization is high, and the treatment cost increases.
Therefore, an economical and environment-friendly treatment process aiming at recycling high-salt-content concentrated water containing complex components and realizing zero discharge of wastewater is provided, and the problem to be solved is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a zero-emission treatment method of high-salt-content wastewater, which comprises a wastewater pretreatment process, a wastewater reduction process and an evaporative crystallization process of high-salt-content concentrated water, wherein after the wastewater pretreatment process, water and salts in the high-salt-content wastewater are recovered through the wastewater reduction process and the evaporative crystallization process of the high-salt-content concentrated water, so that the zero emission of the wastewater is realized, wherein the wastewater pretreatment process comprises the steps of adding a flocculation and/or precipitation reagent, removing heavy metal ions, hardness ions and organic substances in the high-salt-content wastewater through a chemical reactor, and then adjusting the pH of the wastewater to be alkaline; the wastewater reduction process is characterized in that the pretreated wastewater is subjected to preliminary reduction treatment through a medium-pressure reverse osmosis device and a high-pressure reverse osmosis device to form high-pressure reverse osmosis concentrated water, the high-pressure reverse osmosis concentrated water is subjected to deep concentration treatment through a first-stage electric-driven ionic membrane device and a second-stage electric-driven ionic membrane device and then is concentrated into high-salt-content concentrated water, and the wastewater reduction process also recovers water produced in the reduction process to a reuse water tank; and the evaporative crystallization process is to respectively recover the salts in the high-salt-content concentrated water through a nitrate evaporative crystallization device and a salt evaporative crystallization device under the condition of negative pressure or micro-positive pressure to form sodium sulfate and sodium chloride commodity.
According to a preferred embodiment, the operating pressure of the medium-pressure reverse osmosis device is 2.0-3.5 MPa, the membrane element of the medium-pressure reverse osmosis device is made of aromatic polyamide composite material, and the width of the flow channel of the membrane element is 1.60-1.70 mm; the operating pressure of the high-pressure reverse osmosis device is 3.5-4.5 MPa, the material of a membrane element of the high-pressure reverse osmosis device is an aromatic polyamide composite material, and the width of a flow channel of the membrane element is 2.00-2.10 mm. Preferably, the flow channel width of the medium-pressure reverse osmosis device membrane element is 1.65mm, and the flow channel width of the high-pressure reverse osmosis device membrane element is 2.03 mm.
According to a preferred embodiment, the primary and secondary electrically-driven ionic membrane devices comprise an anode and a cathode arranged at an interval, a plurality of membrane pairs consisting of a positive membrane, a negative membrane and a partition plate are regularly arranged between the anode and the cathode, the positive membrane and the negative membrane are homogeneous membranes with low membrane resistance and high performance, the partition plate with uniform fluid state is arranged between the two membranes, and the power supply of the primary and secondary electrically-driven ionic membrane devices adopts a high-frequency direct current power supply with automatically switched positive and negative polarities, utilizes a digital program to control the power supply, adopts adjustable gap high-frequency oscillation to output high-frequency reverse polarity direct current to easily disturb a polarizing layer formed on the surface of the membrane, destroys calcium and magnesium cations with high concentration times in the polarizing layer, and destroys crystallization processes to cause molecular disproportionation of the polarizing layer. The scale inhibition effect is realized, the hydrodynamic condition is optimized, and the power consumption is effectively reduced by 30-50%.
According to a preferred embodiment, the pretreatment process of the wastewater is completed by the following steps: the method comprises the steps of homogenizing and uniformly adjusting the wastewater in an adjusting tank, then sending the wastewater into a high-density tank, sequentially adding lime or sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide into the high-density tank through a dosing device, carrying out flocculation and/or precipitation treatment on the wastewater through a chemical reactor, filtering concentrated water generated after treatment through the chemical reactor through a tubular micro-filter and a filter element filter, then sending the filtered concentrated water into a first intermediate tank, and adjusting the pH value of the wastewater in the first intermediate tank to be 8.0-9.5. Preferably, the aperture of the filter membrane of the tubular micro-filter is 1-5 μm, and substances such as precipitates, coagulation colloids and the like generated by chemical reaction can be further removed.
According to a preferred embodiment, after sludge produced in the high-density tank and sludge produced in the tubular micro-filter are discharged into a sludge tank and subjected to sludge-water separation by a sludge dewatering device, the produced sludge cake is subjected to dry sludge treatment, and the produced water enters the adjusting tank to be mixed with untreated wastewater for recycling treatment.
According to a preferred embodiment, the process for the reduction treatment of the wastewater is completed according to the following steps: the waste water after the preliminary treatment that pond was collected in the middle of first passes through middling pressure reverse osmosis unit carries out preliminary decrement ization and handles the concentrated water of formation middling pressure reverse osmosis and discharge into middling pressure concentrated water pond, the concentrated water of middling pressure reverse osmosis that the concentrated water pond was collected passes through high pressure reverse osmosis unit further carries out preliminary decrement ization and forms high pressure reverse osmosis concentrated water and discharge into high pressure concentrated water pond, middling pressure reverse osmosis unit with the water and the high pressure reverse osmosis product water of middling pressure reverse osmosis unit formation get into the retrieval and utilization water tank behind second grade reverse osmosis unit and the fresh water tank.
According to a preferred embodiment, the high-pressure reverse osmosis concentrated water in the high-pressure concentrated water tank is treated by an activated carbon filter and a resin tank and then discharged into a second intermediate water tank for deep concentration treatment, the pretreated high-pressure reverse osmosis concentrated water in the second intermediate water tank is treated by the first-stage electrically-driven ionic membrane device to form first-stage electrically-driven membrane concentrated water, the first-stage electrically-driven membrane concentrated water enters the second-stage electrically-driven ionic membrane device through a first concentrated water tank for further deep concentration treatment, the first-stage electrically-driven membrane concentrated water is treated by the second-stage electrically-driven ionic membrane device and then concentrated into high-salt concentrated water, the second-stage electrically-driven ionic membrane device is treated and then concentrated into second concentrated water tank, and first-stage electrically-driven produced water treated by the first-stage electrically-driven.
According to a preferred embodiment, the pretreated wastewater in the first intermediate water tank enters a first security filter through a first booster pump, is filtered and then enters the medium-pressure reverse osmosis device, and the security filter element of the first security filter is a three-layer stepped filter element, and the sizes of the three-layer stepped filter element are respectively 10 μm, 15 μm and 20 μm; the medium-pressure reverse osmosis concentrated water in the medium-pressure concentrated water tank enters a second cartridge filter through a second booster pump, is filtered and then enters the high-pressure reverse osmosis device, and a cartridge filter element of the second cartridge filter is a three-layer stepped filter element, wherein the sizes of the three-layer stepped filter element are respectively 5 micrometers, 10 micrometers and 15 micrometers; the pretreated high-pressure reverse osmosis concentrated water in the second intermediate water tank enters a third cartridge filter through a third booster pump, is filtered and then enters the first-stage electric-driven ionic membrane device, a cartridge filter element of the third cartridge filter is a three-layer stepped filter element, and the sizes of the three-layer stepped filter element are respectively 1 mu m, 5 mu m and 10 mu m.
According to a preferred embodiment, the evaporative crystallization process of the high-salt-content concentrated water is completed by the following steps: and (2) carrying out evaporative crystallization on the high-salt-content concentrated water in the second concentrated brine tank by the nitrate evaporative crystallization device under negative pressure or micro positive pressure, carrying out centrifugal separation on the nitrate mother liquor generated by the evaporative crystallization through a frozen nitrate crystallization device after freezing crystallization, returning the nitrate decahydrate generated by centrifugation, carrying out hot melting on the nitrate mother liquor generated by the nitrate evaporative crystallization device, separating sodium sulfate solid through a centrifugal separator, drying to obtain the commercial anhydrous sodium sulfate, carrying out evaporative crystallization on the frozen nitrate mother liquor generated by the centrifugal separation through the frozen nitrate centrifugal separator under negative pressure or micro positive pressure to separate sodium chloride solid through a salt evaporative crystallization device, and drying to obtain the commercial anhydrous sodium chloride.
According to a preferred embodiment, the secondary steam generated by the evaporation of the saltpeter evaporation crystallization device is compressed by a first steam compressor and is heated and pressurized, and the primary heater continuously provides heat energy for the high-salt-content concentrated water preheated by the raw material feeding preheater to reach the boiling point, and the secondary steam generated by the evaporation of the saltpeter evaporation crystallization device is compressed by a second steam compressor and is heated and pressurized by a second heater for circulating heating of the frozen saltpeter mother liquor in the heater (314) to reach the boiling point.
The zero-emission treatment method for the high-salinity wastewater provided by the invention at least has the following advantages:
(1) according to the invention, after the wastewater is subjected to preliminary reduction treatment by adopting the medium-pressure reverse osmosis device and the high-pressure reverse osmosis device, the wastewater is subjected to deep concentration treatment by using the first-stage electrically-driven ionic membrane device and the second-stage electrically-driven ionic membrane device, the separation of treatment liquid in the whole process has no phase change process, the recovery amount of the wastewater can reach more than 95%, only about 5% of high-salt-content concentrated water is produced, the energy consumption required in the evaporative crystallization process is greatly reduced, and the treatment cost of the wastewater can be reduced.
(2) In the evaporative crystallization process, the temperature of the secondary steam is increased by the steam compressor, and the temperature of the feed liquid is increased by using the secondary steam to replace the raw steam to heat the high-salt-content concentrated water, so that the raw steam is not required to be reused, and the consumption of the raw steam can be greatly reduced; on the other hand, through carrying out the evaporative crystallization to the high salt concentration water, sodium sulfate and sodium chloride in the high salt concentration water are retrieved in the separation, collect the comdenstion water that the evaporative crystallization produced and get into the retrieval and utilization water tank, can realize the zero release of the high salt waste water that contains.
(3) Aiming at the problem that organic matters and calcium and magnesium ions are easy to generate scaling and dirt blocking on the surface of a reverse osmosis membrane in the prior art, the invention adopts two measures: firstly, after flocculation and/or precipitation treatment is carried out on the wastewater by adopting a chemical method in the pretreatment process, heavy metal ions, calcium and magnesium ions and partial organic substances are removed, and the pH value of the pretreated wastewater is adjusted to be alkaline, so that the problems of organic contamination and blockage and calcium and magnesium ion scaling on the surface of a reverse osmosis membrane can be avoided when the wastewater enters a reverse osmosis device for treatment; and secondly, the flow channel of the reverse osmosis membrane element is enlarged, so that the problems of ion scaling and organic matter blockage of the reverse osmosis device membrane element are not easy to occur.
Drawings
FIG. 1 is a block diagram of a system for the zero emission treatment process of the present invention;
FIG. 2 is a block diagram of the apparatus of the pretreatment process of the zero-emission treatment method of the present invention;
FIG. 3 is a block diagram of the apparatus of the reduction process of the zero emission treatment method of the present invention;
FIG. 4 is a block diagram of an apparatus for an evaporative crystallization process of the zero-emission treatment method of the present invention.
List of reference numerals
10: the preprocessing unit 20: the reduction unit 30: evaporative crystallization mass-divided salt unit
21: the preliminary reduction unit 22: deep concentration unit 101: adjusting tank
102: high density tank 103: the medicine adding device 104: tubular micro-filter
105: cartridge filter 106: first intermediate pool 107: sludge tank
108: sludge dewatering device 201: secondary reverse osmosis device 202: fresh water tank
203: the recycling water tank 211: medium-pressure reverse osmosis device 212: medium pressure thick water pool
213: high pressure reverse osmosis unit 214: the high-pressure concentrated water tank 221: activated carbon filter
222: resin tank 223: second intermediate pool
224: primary electrically-driven ionic membrane device 225: first strong brine tank
226: two-stage electrically driven ionic membrane device 227: second strong brine tank
301: raw material feed preheater 302: nitre evaporation crystallization device 303: saltpeter thickener
304: centrifugal separator 305: nitre mother liquor tank 306: first dryer
307: first metering and packaging device 308: nitre mother liquor pump 309: freezing nitre crystallization device
310: first settler 311: frozen saltpeter centrifuge 312: frozen nitre mother liquid tank
313: cold nitre mother liquor pump 314: the heater 315: salt evaporation crystallization device
316: first steam generating device 317: first heater 318: first vapor compressor
319: cooling water system 320: the freezer 321: cooling device
322: the vacuum system 323: the saltpeter circulating pump 324: second steam generation device
325: second heater 326: the second vapor compressor 327: circulating pump
328: second settler 329: salt centrifuge 330: second dryer
331: second metering and packaging device 332: cold nitre circulating pump
Detailed Description
The following detailed description is made with reference to the accompanying drawings and examples.
The high-salinity wastewater refers to oil refining wastewater, coal chemical wastewater, circulating system sewage, reverse osmosis concentrated water, wastewater containing complex components in a sewage treatment plant and the like, the TDS of the high-salinity wastewater is 5000-10000 mg/L, namely the total soluble solid content in the 1L high-salinity wastewater is 5000-10000 mg.
The invention provides a zero-emission treatment method of high-salt-content wastewater, which has the general inventive concept that heavy metal ions, calcium and magnesium ions and partial organic substances in the wastewater are removed through pretreatment, then the high-salt-content wastewater is subjected to preliminary reduction treatment through a reverse osmosis device to recover partial water in the wastewater, reverse osmosis concentrated water is subjected to deep concentration treatment through an electric drive membrane device, the high-salt-content concentrated water formed after the concentration treatment is sent to an evaporative crystallization salt separation device, and salts in the high-salt-content concentrated water are separated and recovered through the evaporative crystallization salt separation device, so that the zero emission of the wastewater and the recovery and reutilization of solid salts are realized. The idea provided by the invention can enable the recovery rate of the wastewater to reach more than 95 percent, greatly reduce the treatment capacity of the evaporative crystallization device on the high-salt-content concentrated water, and enable the water quantity not to have phase change in the separation process, thereby reducing the energy consumption in the treatment process. The invention is not limited to the preliminary reduction treatment of the high-salt-content wastewater by using a medium-pressure reverse osmosis device and a high-pressure reverse osmosis device, and the device in the preliminary reduction treatment process can also be an ultrahigh-pressure reverse osmosis device. The invention is not limited to the deep concentration treatment of the high-pressure reverse osmosis concentrated water by using the first-stage electrically-driven ionic membrane device and the second-stage electrically-driven ionic membrane device, and the devices in the deep concentration treatment process can also be three-stage electrically-driven ionic membrane devices, even multi-stage electrically-driven ionic membrane devices.
The zero-emission treatment method of the high-salt-content wastewater provided by the invention comprises a wastewater pretreatment process, a wastewater reduction process and an evaporation crystallization process of high-salt-content concentrated water. FIG. 1 shows a block diagram of a system for the zero emission treatment process of the present invention. As shown in figure 1, the system used in the zero-emission treatment method of the high-salinity wastewater comprises a pretreatment unit 10, a reduction unit 20 and an evaporative crystallization and mass-separation salt unit 30. The reduction unit 20 in turn comprises a preliminary reduction unit 21 and a depth concentration unit 22. After the pretreatment process, the water and the salts in the wastewater with high salt content can be recovered through the wastewater reduction process and the evaporative crystallization process of the concentrated water with high salt content, so that zero emission of the wastewater and recycling of the salts are realized. Wherein, the pretreatment process of the wastewater is to remove heavy metal ions, hardness ions and organic substances in the wastewater with high salt content by adding a flocculating and/or precipitating agent and a chemical reactor. After heavy metal ions, hardness ions and organic substances are removed, the pH value of the wastewater is adjusted to be alkaline. The wastewater reduction process is to perform preliminary reduction treatment on the pretreated wastewater through a medium-pressure reverse osmosis device 211 and a high-pressure reverse osmosis device 213 to form high-pressure reverse osmosis concentrated water. The high-pressure reverse osmosis concentrated water is subjected to deep concentration treatment by a first-stage electrically-driven ionic membrane device 224 and a second-stage electrically-driven ionic membrane device 226 and then is concentrated into high-salt-content concentrated water. The wastewater reduction process also includes recovering the water produced during the reduction process to a reuse water tank 203. The evaporative crystallization process is to respectively recover the salts in the high-salt-content concentrated water through a nitrate evaporative crystallization device 302 and a salt evaporative crystallization device 315 under the condition of negative pressure or micro positive pressure, and form sodium sulfate and sodium chloride commodity through the processes of drying and the like.
According to a preferred embodiment, the operating pressure of the medium-pressure reverse osmosis device 211 is 2.0 to 3.5 MPa. The medium-pressure reverse osmosis device 211 is made of aromatic polyamide composite materials. The flow channel width of the medium-pressure reverse osmosis device 211 membrane element is 1.60-1.70 mm. The operating pressure of the high-pressure reverse osmosis device 213 is 3.5-4.5 MPa. The material of the membrane element of the high-pressure reverse osmosis device 213 is aromatic polyamide composite material. The width of a flow channel of the high-pressure reverse osmosis device 213 membrane element is 2.00-2.10 mm. . Preferably, the flow channel width of the medium-pressure reverse osmosis device 211 membrane element is 1.65 mm. The flow channel width of the high-pressure reverse osmosis device 213 membrane element is 2.03 mm. Preferably, the medium-pressure reverse osmosis device 211 adopts a special concentrated anti-pollution medium-pressure membrane element GTR 3-8040F-65. The high-pressure reverse osmosis device 213 adopts a special concentrated anti-pollution high-pressure membrane element GTR 4-8040F-80. The medium-pressure reverse osmosis device 211 membrane element and the high-pressure reverse osmosis device 213 membrane element are made of aromatic polyamide composite materials, and can remove at least 90% of target heavy metals in wastewater. Specifically, the aromatic polyamide membrane can also remove cadmium, chromium, copper, iron, nickel, zinc, manganese, magnesium and other similar heavy metals in the wastewater. The aramid film has a high removal rate of heavy metals, and in particular is capable of removing at least 99% of arsenic, at least 98% of nickel, at least 97% of manganese, at least 99% of magnesium, 94% of chromium, and at least 80% of calcium, copper, and zinc from wastewater. On the other hand, the aromatic polyamide membrane also has high salt rejection rate, and can efficiently remove nano-scale pollutants with molecular weight more than 100, such as anions. The medium-pressure reverse osmosis device 211 and the high-pressure reverse osmosis device 213 carry out preliminary reduction treatment on the high-salt-content wastewater at the pressure of 2.0-4.5 MPa, and compared with the conventional reverse osmosis treatment, the treatment efficiency is higher.
According to a preferred embodiment, the primary and secondary electrically driven ionic membrane devices 224 and 226 include an anode and a cathode spaced apart. Between the anode and the cathode are regularly arranged a plurality of membrane pairs consisting of an anode membrane, a cathode membrane and a separator. The positive membrane and the negative membrane are homogeneous membranes with low membrane resistance and high performance. A clapboard with uniform flow state is arranged between the two films. The power supply of the first-stage electrically-driven ionic membrane device 224 and the second-stage electrically-driven ionic membrane device 226 adopts a high-frequency direct-current power supply with positive and negative polarities automatically switched, and the power supply is controlled by a digital program. The primary electrically-driven ionic membrane device 224 and the secondary electrically-driven ionic membrane device 226 adopt adjustable gap high-frequency oscillation to output high-frequency reversed polarity direct current to disturb a polarization layer which is easy to form on the membrane surface, destroy calcium and magnesium cations with high concentration times in the polarization layer, and destroy the molecular disproportionation of the polarization layer in the crystallization process. The first-stage electrically-driven ionic membrane device 224 and the second-stage electrically-driven ionic membrane device 226 can play a role in physical scale inhibition, optimizing hydrodynamic conditions and effectively reducing power consumption by 30-50%.
According to a preferred embodiment, the process for the pretreatment of wastewater is carried out as follows: the wastewater is homogenized and volume-regulated in a regulating tank 101 and then sent to a high-density tank 102. Lime or sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide are sequentially added into the high-density tank 102 through a dosing device 103, and flocculation and/or precipitation treatment is carried out on the wastewater through a chemical reactor. The concentrated water produced after the treatment in the chemical reactor is filtered by the tubular micro-filter 104 and the cartridge filter 105 and then enters the first intermediate water tank 106. Preferably, the aperture of the filter membrane of the tubular micro-filter is 1-5 μm, and substances such as precipitates, coagulation colloids and the like generated by chemical reaction can be further removed. And adjusting the pH value of the wastewater in the first intermediate water tank 106 to 8.0-9.5. The alkaline environment is helpful for inhibiting the scaling of organic matters and calcium and magnesium ions on the surface of the reverse osmosis membrane. Sludge produced in the high-density tank 102 and sludge produced in the tubular micro-filter 104 are discharged into a sludge tank 107. Sludge in the sludge tank 107 is subjected to sludge-water separation by a sludge dewatering device 108. The produced mud cake is treated by dry mud. The produced water enters the conditioning tank 101 to be mixed with untreated wastewater for recycling treatment.
According to a preferred embodiment, the high density tank 102 contains a chemical reactor for removing organic, colloidal, and hardness ions. The chemical reactor can not only fully mix the medicament with the wastewater at a high speed, but also is beneficial to generating floc and can more effectively separate solid from liquid. The chemical reactor utilizes the column plate to make the eddy micro-power generated by water flow greatly facilitate the adsorption of impurities by flocs, so that the effect of deep purification can be achieved by adding a small amount of flocculant. On the other hand, the chemical reactor can also ensure that a small amount of flocculant added can generate large flocs with large fluffs and strong adsorption capacity to the maximum extent. The chemical reactor ensures high utilization rate of the added medicament and can reduce the treatment cost of the wastewater.
According to the invention, in the pretreatment process, a chemical method is adopted to remove heavy metal ions, calcium, magnesium and other hardness ions, and simultaneously remove most COD and organic colloidal substances, so that the problems of organic matter pollution and calcium, magnesium and scale formation can be avoided when the wastewater is subjected to next treatment. On the other hand, the pH value of the pretreated wastewater is adjusted to be 8.0-9.5 in an alkaline environment, so that the problems of scaling on the surface of the reverse osmosis membrane and organic matter pollution can be further solved.
According to a preferred embodiment, the process for the reduction treatment of wastewater is carried out as follows: the pretreated wastewater collected by the first intermediate water basin 106 is subjected to a preliminary reduction treatment by the medium pressure reverse osmosis device 211. The medium pressure reverse osmosis concentrate water formed by the medium pressure reverse osmosis device 211 is discharged into a medium pressure concentrate tank 212. The medium pressure reverse osmosis concentrated water collected by the medium pressure concentrated water tank 212 is further subjected to preliminary reduction treatment by the high pressure reverse osmosis device 213. The high-pressure reverse osmosis concentrated water formed by the treatment of the high-pressure reverse osmosis device 213 is discharged into the high-pressure concentrated water tank 214. The medium-pressure reverse osmosis produced water and the high-pressure reverse osmosis produced water formed by the medium-pressure reverse osmosis device 211 and the high-pressure reverse osmosis device 213 are discharged into the secondary reverse osmosis device 201. The medium-pressure reverse osmosis produced water and the high-pressure reverse osmosis produced water enter a reuse water tank 203 after passing through a secondary reverse osmosis device 201 and a fresh water tank 202. The high-pressure reverse osmosis concentrated water in the high-pressure concentrated water tank 214 is treated by the activated carbon filter 221 and the resin tank 222 and then discharged into the second intermediate water tank 223 to be subjected to deep concentration treatment. The pretreated high-pressure reverse osmosis concentrated water in the second intermediate water tank 223 is treated by the first-stage electrically-driven ionic membrane device 224 to form first-stage electrically-driven membrane concentrated water. The first-stage electric-driven membrane concentrated water enters the second-stage electric-driven ionic membrane device 226 through the first concentrated brine tank 225 for further deep concentration treatment. The first-stage electrically-driven membrane concentrated water is treated by the second-stage electrically-driven ionic membrane device 226 and then concentrated into high-salt-content concentrated water, and the high-salt-content concentrated water enters a second concentrated brine tank 227. The primary electrically driven produced water formed after treatment by the primary electrically driven ionic membrane device 224 is discharged into the secondary reverse osmosis device 201. The primary electric drive produced water enters a reuse water tank 203 through a secondary reverse osmosis device 201 and a fresh water tank 202. The activated carbon filter 221 may adsorb chlorine that is not removed in the preliminary reduction process, and at the same time, adsorb small molecular organic matter, colloids, and heavy metal ions. The resin tank 222 has ion exchange resin for adsorbing chemical ions in the solution treated by the activated carbon filter 221. The high-pressure reverse osmosis concentrated water is pretreated by the activated carbon filter 221 and the resin tank 222 before entering the first-stage electrically-driven ionic membrane device 224, so that the high-pressure reverse osmosis concentrated water can meet the water inlet requirement of the first-stage electrically-driven ionic membrane device 224, and the damage to the first-stage electrically-driven ionic membrane device 224 is reduced.
According to a preferred embodiment, the wastewater pretreated in the first intermediate water tank 106 is introduced into the first safety filter through the first booster pump and then introduced into the medium-pressure reverse osmosis device 211. The security filter element of the first security filter is a three-layer stepped filter element. The sizes of the three-layer stepped filter element are respectively 10 mu m, 15 mu m and 20 mu m. The medium-pressure reverse osmosis concentrated water in the medium-pressure concentrated water tank 212 enters a second cartridge filter through a second booster pump, is filtered and then enters the high-pressure reverse osmosis device 213. The security filter element of the second security filter is a three-layer stepped filter element. The sizes of the three-layer stepped filter element are respectively 5 mu m, 10 mu m and 15 mu m. The high-pressure reverse osmosis concentrated water after pretreatment in the second intermediate water tank 223 enters a third cartridge filter through a third booster pump, is filtered, and then enters the first-stage electrically-driven ionic membrane device 224. The cartridge filter element of the third cartridge filter is a three-layer stepped filter element. The sizes of the three-layer stepped filter element are respectively 1 mu m, 5 mu m and 10 mu m. The cartridge filter may be used to remove fine quartz sand, activated carbon particles, etc. to ensure that the waste water is less damaging to the next device when entering the next device. The filter elements of the first security filter, the second security filter and the third security filter adopt three-layer stepped filter elements, so that small particulate matters in the wastewater can be removed step by step, and the filter elements of the first security filter, the second security filter and the third security filter are reduced in size in sequence, so that smaller particulate matters which cannot be removed in the previous step can be further removed.
According to a preferred embodiment, after being treated by the medium-pressure reverse osmosis device 211, more than 70% of the inlet water forms medium-pressure reverse osmosis produced water and enters the reuse water tank 203, and the rest less than 30% forms medium-pressure reverse osmosis concentrated water. The medium-pressure reverse osmosis concentrated water is used as the inlet water of the high-pressure reverse osmosis device 213. After being treated by the high-pressure reverse osmosis device 213, more than 65 percent of the inlet water forms high-pressure reverse osmosis produced water and enters the reuse water tank 203, and the rest less than 35 percent forms high-pressure reverse osmosis concentrated water. The high pressure reverse osmosis concentrated water is used as the inlet water of the first stage electrically driven ionic membrane device 224. After being treated by the first-stage electric-driven ionic membrane device 224, more than 75 percent of the inlet water forms first-stage electric-driven produced water and enters the reuse water tank 203, and the rest less than 25 percent forms first-stage electric-driven membrane concentrated water. The first-stage electrically-driven membrane concentrated water is used as the inlet water of the second-stage electrically-driven ionic membrane device 226.
After the preliminary reduction and the advanced concentration treatment, more than 95 percent of the wastewater can be recycled, and less than 5 percent of the wastewater is concentrated into high-salt-content concentrated water.
According to a preferred embodiment, the evaporative crystallization process of the high-salt-content concentrated water is completed according to the following steps: the high-salinity concentrated water in the second concentrated brine tank 227 is evaporated and crystallized by the nitrate evaporation and crystallization device 302 under negative pressure or slightly positive pressure. And (3) freezing and crystallizing nitrate mother liquor generated by evaporating and crystallizing high-salt-content concentrated water by using a freezing nitrate crystallizing device 309, then centrifugally separating by using a freezing nitrate centrifugal separator 311, returning decahydrate generated by centrifugation to be thermally melted with solid nitrate-containing liquid generated by a nitrate evaporating and crystallizing device 302, then separating a commodity sodium sulfate solid by using a centrifugal separator 304, and drying to obtain the commodity anhydrous sodium sulfate. The frozen nitre mother liquor generated by the centrifugation of the frozen nitre centrifugal separator 311 is evaporated and crystallized by a salt evaporation crystallization device 315 under negative pressure or micro-positive pressure to separate sodium chloride solid, and the sodium chloride solid is dried to obtain the commercial anhydrous sodium chloride. Preferably, the secondary steam generated by the evaporation of the nitrate evaporation crystallization device 302 is compressed and raised in pressure by the first steam compressor 318, and continuously provides heat energy for the high-salt-content concentrated water preheated by the raw material feed preheater 301 by the first heater 317 to reach the boiling point. The secondary steam generated by the evaporation of the salt evaporation crystallization device 315 is compressed by the second steam compressor 326 and is heated by the second heater 325 after the temperature and the pressure are increased, and the secondary steam is used for circularly heating the preheated high-salt-content concentrated water in the heater 314 to reach the boiling point. Meanwhile, the evaporative crystallization process of the high-salt-content concentrated water recovers condensed water in the evaporative crystallization process to the reuse water tank 203.
Through the evaporation crystallization process, the purity of the separated sodium sulfate commodity is about 96%, and the purity of the separated sodium chloride commodity is more than 98%. The zero-discharge treatment method for the high-salt-content wastewater provided by the invention not only can realize zero discharge of the wastewater, but also can reduce the treatment cost of the high-salt-content wastewater. The invention provides a high-salt-content wastewater zero-emission treatment method with strong industrial applicability.
Example 1
Take the structure of the primary electrically driven ionic membrane device 224 and the secondary electrically driven ionic membrane device 226 used in the present invention as an example.
The primary and secondary electrically-driven ionic membrane devices 224 and 226 include an anode and a cathode spaced apart from each other. Between the anode and the cathode are regularly arranged a plurality of membrane pairs consisting of an anode membrane, a cathode membrane and a separator. The positive membrane and the negative membrane are homogeneous membranes with low membrane resistance and high performance. A clapboard with uniform flow state is arranged between the two films. The power supply of the first-stage electrically-driven ionic membrane device 224 and the second-stage electrically-driven ionic membrane device 226 adopts a high-frequency direct-current power supply with positive and negative polarities automatically switched, and the power supply is controlled by a digital program. The primary electrically-driven ionic membrane device 224 and the secondary electrically-driven ionic membrane device 226 adopt adjustable gap high-frequency oscillation to output high-frequency reversed polarity direct current to disturb a polarization layer which is easy to form on the membrane surface, destroy calcium and magnesium cations with high concentration times in the polarization layer, and destroy the molecular disproportionation of the polarization layer in the crystallization process. The first-stage electrically-driven ionic membrane device 224 and the second-stage electrically-driven ionic membrane device 226 can play a role in physical scale inhibition, optimizing hydrodynamic conditions and effectively reducing power consumption by 30-50%.
The diaphragm is an ion exchange membrane. Preferably, the cathode membrane is a cation exchange membrane and the anode membrane is an anion exchange membrane. Under the action of an external electric field, the cation exchange membrane only allows cationic ions to pass through, and the anion exchange membrane only allows anionic ions to pass through. Uncharged molecules and organic matters cannot permeate the diaphragm, and the directional migration of charged ions can be realized. A concentrated saline chamber and a dilute saline chamber are formed between each pair of membrane pairs, so that the concentration and the desalination of high-content saline in water are realized.
According to a preferred embodiment, the electrically driven ionic membrane device is basically constructed by a membrane stack, mainly comprising a locking frame, a feeding frame, a cationic and anionic membrane, a partition plate, a water distribution groove, a partition net, an electrode and a polar chamber, a press and the like. The thickness of the separator is 0.5-2.0 mm. The membrane stack is composed of a plurality of membrane pairs which are alternately arranged, and a concentration chamber and a desalting chamber are composed of anion and cation membranes and net partition plates. And the pretreated high-salt-content concentrated water enters a compartment of an electrically-driven ionic membrane device, under the action of an external direct current electric field, anions and cations in the high-salt-content concentrated water move directionally, the anions move towards the anode direction, and the cations move towards the cathode direction. Because the ion exchange membrane has selective permeability, the fixed exchange groups of the cation exchange membrane are negatively charged, thereby allowing cations in water to pass through and blocking anions; the fixed exchange groups of the anion exchange membrane are positively charged, so that anions in water are allowed to pass through and cations are blocked, ions in the fresh water compartment are caused to migrate into the concentrated water compartment, and ions in the high-salinity concentrated water are separated from the saline solution, so that concentrated water and desalted fresh water are obtained.
Example 2
Take the pretreatment process of wastewater as an example.
As shown in FIG. 2, the apparatus for the pretreatment process of wastewater at least comprises a regulating tank 101, a high density tank 102, a dosing apparatus 103, a tubular micro-filter 104, a filter element filter 105, a first intermediate water tank 106, a sludge tank 107 and a sludge dewatering apparatus 108.
The method comprises the steps of feeding wastewater sent by each pipeline into a high-density tank 102 through a lifting pump, adding lime or sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide into the wastewater in the high-density tank 102 through a dosing device 103, preferably, adding an amount of an additive which is not too large, adjusting the amount of the additive according to actual conditions of water quality, and influencing the service life of a membrane, preferably, preparing the sodium hydroxide into a solution with a concentration of 20%, adding 1.5 g/L, preparing the sodium carbonate into a solution with a concentration of 15%, adding 3.0 g/L, preparing the polyaluminium chloride into a solution with a concentration of 20%, adding 30 mg/L, preparing the polyacrylamide into a solution with a concentration of 0.3%, adding 3 mg/L, performing chemical agent reaction with the polyaluminium chloride into a solution with a concentration of 20%, adding the polyaluminium chloride into a solution with a concentration of 30 mg/L, preparing the polyacrylamide into a solution with a concentration of 0.3%, adding the sodium carbonate into a lower layer, filtering the lower layer, discharging the wastewater into a lower layer, discharging the lower layer, collecting the lower layer, discharging the wastewater into a tubular sludge filter 104, performing a tubular sludge filter element 106, performing a sludge settling reaction, and collecting the sludge layer, wherein the wastewater is discharged into a tubular sludge filter element 106, discharging the lower layer, discharging the sludge from a tubular sludge, discharging the lower layer, collecting the sludge layer, discharging the sludge, discharging the primary sludge, discharging the tubular filter element, discharging the sludge, collecting the sludge, discharging the sludge.
The pretreatment process of the invention can obtain clear water without heavy metal ions, hardness ions and organic matters through flocculation and/or precipitation reaction in the high-density tank 102 and further filtration of concentrated water generated by the reaction through the tubular micro-filter 104 and the filter element filter 105, and can prevent the organic matters and calcium and magnesium ions from scaling and fouling on the surface of the reverse osmosis membrane by adjusting the pH of the clear water to be an alkaline environment in the first intermediate water tank 106.
Example 3
Take the reduction treatment process of wastewater as an example.
The wastewater reduction process comprises a primary reduction process and a deep concentration process. As shown in fig. 3, the devices of the preliminary reduction process include at least a medium-pressure reverse osmosis device 211, a medium-pressure concentrated water tank 212, a high-pressure reverse osmosis device 213, and a high-pressure concentrated water tank 214. The apparatus of the deep concentration process includes at least an activated carbon filter 221, a resin tank 222, a second intermediate water tank 223, a primary electrically-driven ionic membrane apparatus 224, a first concentrated salt water tank 225, a secondary electrically-driven ionic membrane apparatus 226, and a second concentrated salt water tank 227. The apparatus for the abatement process further comprises a secondary reverse osmosis unit 201, a fresh water tank 202 and a reuse water tank 203.
The pretreated wastewater collected in the first intermediate water tank 106 is subjected to preliminary reduction treatment by the medium-pressure reverse osmosis device 211 and the high-pressure reverse osmosis device 213. The medium pressure reverse osmosis unit 211 is connected to the first intermediate water sump 106 via a first booster pump and a first safety filter. The medium-pressure reverse osmosis concentrated water treated by the medium-pressure reverse osmosis device 211 is discharged into a medium-pressure concentrated water tank 212. The medium-pressure reverse osmosis concentrated water in the medium-pressure concentrated water tank 212 enters a second cartridge filter through a second booster pump, is filtered and then enters the high-pressure reverse osmosis device 213. The high-pressure reverse osmosis concentrated water treated by the high-pressure reverse osmosis device 213 enters the high-pressure concentrated water tank 214 for deep concentration treatment. The concentrated water in the high-pressure concentrated water tank 214 is further subjected to removal of hardness ions in the concentrated water by an activated carbon filter 221 and a resin tank 222, and then enters a second intermediate water tank 223. The high-pressure reverse osmosis concentrated water after pretreatment in the second intermediate water tank 223 enters a third cartridge filter through a third booster pump, is filtered, and then enters the first-stage electrically-driven ionic membrane device 224. The concentrated water in the second intermediate water tank 223 is subjected to deep concentration treatment by the first-stage electrically-driven ionic membrane device 224 and the second-stage electrically-driven ionic membrane device 226 to form high-salinity concentrated water, and the high-salinity concentrated water enters the second concentrated brine tank 227. Preferably, the produced water formed after being treated by the medium-pressure reverse osmosis device 211, the high-pressure reverse osmosis device 213 and the first-stage electrically-driven ionic membrane device 224 enters the second-stage reverse osmosis device 201, and the produced water enters the reuse water tank 203 for reuse after passing through the fresh water tank 202.
Preferably, the medium-pressure reverse osmosis device 211 is made of an aromatic polyamide composite material, the operating pressure is 2.0-3.5 MPa, the medium-pressure reverse osmosis device 211 can intercept 97.5% of salt substances, wastewater with the average TDS of 6500 mg/L can be concentrated to the TDS of more than 21600 mg/L, after being treated by the medium-pressure reverse osmosis device 211, more than 70% of inlet water forms medium-pressure reverse osmosis produced water, the medium-pressure reverse osmosis produced water enters the reuse water tank 203 after passing through the secondary reverse osmosis device 201 and the fresh water tank 202, the remaining 30% or less of the medium-pressure reverse osmosis concentrated water enters the high-pressure reverse osmosis device 213 for further desalination and concentration, the high-pressure reverse osmosis device 213 is made of the aromatic polyamide composite material, the operating pressure is 3.5-4.5 MPa, the high-pressure reverse osmosis device 213 can intercept 97.2% of the salt substances, the wastewater with the average TDS of 21600 mg/L can be concentrated to the TDS of more than 50000 mg/L, after being treated by the high-pressure reverse osmosis device 213, the high-pressure reverse osmosis device can intercept 97.65% of the salt substances, the wastewater with the average TDS of 21600 mg/L.
Preferably, the high-pressure reverse osmosis concentrated water enters the first-stage electrically-driven ionic membrane device 224 for deep concentration treatment, the water supply pressure is 0.20MPa, the first-stage electrically-driven ionic membrane device 224 can retain 96.2% of salt substances, the wastewater with the average TDS of 50000 mg/L can be concentrated to the TDS larger than 200000 mg/L, after the wastewater is treated by the first-stage electrically-driven ionic membrane device 224, more than 75% of the inlet water forms first-stage electrically-driven product water, the first-stage electrically-driven product water passes through the second-stage reverse osmosis device 201 and the fresh water tank 202 and then enters the reuse water tank 203, the rest 25% or less enters the second-stage electrically-driven ionic membrane device 226 for further deep concentration treatment, after the deep concentration treatment is carried out by the two-stage electrically-driven ionic membrane device, more than 95% of the wastewater can be recycled, and less.
According to the invention, the wastewater is subjected to preliminary reduction through the medium-pressure reverse osmosis device 211 and the high-pressure reverse osmosis device 213 and then subjected to deep concentration treatment through the primary electrically-driven ionic membrane device 224 and the secondary electrically-driven ionic membrane device 226, the recovery amount of the wastewater in the whole process can reach more than 95%, only about 5% of high-salt-content concentrated water needs to be subjected to an evaporative crystallization process, the energy consumption required in the evaporative crystallization process is greatly reduced, and the treatment cost of the wastewater can be reduced.
Example 4
Take the evaporation crystallization process of high salt-containing concentrated water as an example.
As shown in FIG. 4, the device of the evaporative crystallization process of high salt-containing concentrated water at least comprises a raw material feed preheater 301, a saltpeter evaporative crystallization device 302, a saltpeter thickener 303, a centrifugal separator 304, a saltpeter mother liquor tank 305, a first dryer 306, a first metering and packaging device 307, a saltpeter mother liquor pump 308, a frozen saltpeter crystallization device 309, a first settler 310, a frozen saltpeter centrifugal separator 311, a frozen saltpeter mother liquor tank 312, a cold saltpeter mother liquor pump 313, a heater 314, a salt evaporative crystallization device 315, a first steam generation device 316, the system comprises a first heater 317, a first steam compressor 318, a cooling water system 319, a refrigerator 320, a cooler 321, a vacuum system 322, a saltpeter circulating pump 323, a second raw steam device 324, a second heater 325, a second steam compressor 326, a circulating pump 327, a second settler 328, a salt centrifugal separator 329, a second dryer 330, a second metering and packaging device 331 and a saltpeter circulating pump 332.
The high-salinity concentrated water in the second concentrated brine tank 227 enters the raw material feed preheater 301 through the fourth booster pump, and enters the nitrate evaporative crystallization device 302 after being preheated. The nitrate evaporation crystallization device 302 is communicated with a vacuum system 322, so that negative pressure or slight positive pressure is kept in the nitrate evaporation crystallization device 302. The nitrate evaporative crystallization device 302, a first steam compressor 318, a first heater 317 and a raw material feed preheater 301 form a heat supply circulation system. The initial energy consumption for heating is provided by the first raw steam plant 316. The first heater 317 is connected by a nitrate circulating pump 323 to heat the nitrate evaporative crystallization apparatus 302. The low temperature exhaust steam from the nitrate evaporative crystallization unit 302 is then compressed by a first steam compressor 318 and heated by a first heater 317 for preheating of the feed preheater 301. The nitrate evaporative crystallization device continuously carries out water volume evaporative concentration under the state of negative pressure or micro positive pressure, and the temperature of the high-salt-content concentrated water is maintained at about 110 ℃. The solid-liquid mixture after evaporation and crystallization enters a centrifugal separator 304 through a nitrate thickener 303. The separated nitre mother liquor enters a nitre mother liquor tank 305, then enters a frozen nitre crystallization device 309 through a nitre mother liquor pump 308, and enters a first settler 310 for adjustment after low-temperature crystallization. The frozen saltpeter crystallization device 309 is connected with a cooler 321. The frozen saltpeter crystallization device 309 is kept at a low temperature by a saltpeter circulation pump 332. The frozen nitrate crystallization device 309 is connected with a refrigerator 320 and a cooling water system 319 through a cooler 321 for circulating cooling, so that the internal mother liquor reaches-10 to-5 ℃. The coolant in the first settler 310 is centrifuged by a frozen nitrate centrifuge 311 to produce nitrate decahydrate and a frozen nitrate mother liquor. The sodium sulfate decahydrate is returned again to be mixed with the sodium sulfate liquid generated by the sodium sulfate evaporative crystallization device 302 in a hot melting way, and then the sodium sulfate is separated by a centrifugal separator 304. The separated sodium sulfate is dried by a first dryer 306 and then enters a first metering and packaging device 307. The frozen nitre mother liquor enters a frozen nitre mother liquor tank 312 and then enters a salt evaporation crystallization device 315 through a cold nitre mother liquor pump 313.
The frozen nitre mother liquor enters a heater 314 for preheating through a frozen nitre mother liquor tank 312 and a frozen nitre mother liquor pump 313, and then enters a salt evaporation crystallization device 315. The salt evaporation crystallization device 315 is in communication with a vacuum system 322 to maintain a negative or slightly positive pressure within the salt evaporation crystallization device 315. The initial heat of heating of the salt evaporative crystallization device 315 comes from the second steam generation device 324 and is heated by the second heater 325. The salt evaporation crystallization device 315 is connected with the second heater 325 through a circulating pump 327 to heat the salt evaporation crystallization device 315. The salt evaporation crystallization device 315, a second vapor compressor 326, a second heater 325 and a heater 314 form a heat supply circulation system. The low-temperature dead steam generated by the salt evaporation and crystallization device 315 is compressed by the second steam compressor 326 and heated by the second heater 325 for preheating the liquid inside the heater 314. The salt evaporation crystallization device 315 continuously performs water evaporation and concentration in a negative pressure or slightly positive pressure state. The product after salt evaporation and crystallization enters a salt centrifugal separator 329 through a second settler 328, and then enters a second metering and packaging device 331 after being dried by a second dryer 330. The finally formed mixed salt accounts for less than 5 percent of the total salt amount, is evaporated into salt mud, is dehydrated by dehydration equipment and is stockpiled. Meanwhile, the condensed water in the evaporative crystallization process is recycled to the reuse water tank 203.
The zero-discharge treatment method can recover various salts besides high-quality water, not only can greatly reduce the quantity of final mixed salt and save the disposal cost of solid waste, but also can take the recovered salts with the purity of more than 96 percent as secondary commercial salt for sale, and can further reduce the treatment cost of wastewater. On the other hand, the high-efficiency deep concentration and MVR evaporation technology is adopted to replace multi-effect evaporation, so that a large amount of energy consumption can be saved, meanwhile, the salts such as sodium sulfate, sodium chloride and the like in the salt solution can be recovered, the economic applicability is high, and the high-salt-content wastewater zero-emission treatment process is affordable for enterprises. The invention also creates a new way for recycling water resources for water resource deficient areas.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents.

Claims (8)

1. A zero discharge treatment method of high-salt-content wastewater comprises a pretreatment process of the wastewater, a reduction process of the wastewater and an evaporative crystallization process of high-salt-content concentrated water, and is characterized in that,
the wastewater reduction process is characterized in that the pretreated wastewater is subjected to preliminary reduction treatment through a medium-pressure reverse osmosis device (211) and a high-pressure reverse osmosis device (213) to form high-pressure reverse osmosis concentrated water, the high-pressure reverse osmosis concentrated water is subjected to deep concentration treatment through a first-stage electric-driven ionic membrane device (224) and a second-stage electric-driven ionic membrane device (226) and then is concentrated into high-salt-content concentrated water, and the wastewater reduction process also recovers water produced in the reduction process to a reuse water tank (203);
the primary electric driven ionic membrane device (224) and the secondary electric driven ionic membrane device (226) comprise an anode and a cathode which are arranged at intervals, a plurality of membrane pairs which are formed by combining a positive membrane, a negative membrane and a partition plate are regularly arranged between the anode and the cathode, the positive membrane and the negative membrane are homogeneous membranes, the partition plate with uniform fluid state is arranged between the two membranes, and the power supply of the primary electric driven ionic membrane device (224) and the secondary electric driven ionic membrane device (226) adopts a high-frequency direct current power supply with positive and negative polarities which are automatically switched and utilizes a digital program to control the power supply, wherein,
the primary electrically-driven ionic membrane device (224) and the secondary electrically-driven ionic membrane device (226) adopt adjustable gap high-frequency oscillation to output high-frequency reversed polarity direct current to disturb a polarizing layer which is easy to form on the surface of the membrane, destroy calcium and magnesium cations with high concentration times in the polarizing layer, and destroy the molecular disproportionation of the polarizing layer in the crystallization process;
the evaporative crystallization process comprises the steps of respectively recovering salts in the high-salt-content concentrated water through a nitrate evaporative crystallization device (302) and a salt evaporative crystallization device (315) under the condition of negative pressure or micro-positive pressure to form sodium sulfate commodity and sodium chloride commodity;
the evaporation crystallization process of the high-salt-content concentrated water is completed according to the following steps:
high-salt-content concentrated water in a second concentrated brine tank (227) is subjected to evaporative crystallization by a nitrate evaporative crystallization device (302) under negative pressure or micro-positive pressure, nitrate mother liquor generated by evaporative crystallization is subjected to freezing crystallization by a freezing nitrate crystallization device (309) and then is subjected to centrifugal separation by a freezing nitrate centrifugal separator (311), decahydrate generated by centrifugation returns to be thermally melted with solid nitrate-containing liquid generated by the nitrate evaporative crystallization device (302), sodium sulfate is separated by the centrifugal separator (304) and then is dried to obtain commercial sodium sulfate,
the frozen nitre mother liquor generated by the centrifugation of the frozen nitre centrifugal separator (311) is evaporated, crystallized and separated out sodium chloride by the salt evaporation crystallization device (315) under negative pressure or micro-positive pressure, and then is dried to obtain commercial sodium chloride, wherein,
after secondary steam generated by evaporation of the saltpeter evaporation crystallization device (302) is compressed and raised in temperature and pressure by a first steam compressor (318), heat energy is continuously provided for high-salt-content concentrated water preheated by a raw material feeding preheater (301) by a first heater (317),
the secondary steam generated by the evaporation of the salt evaporation crystallization device (315) is compressed by a second steam compressor (326) and is used for heating the frozen nitre mother liquor in the heater (314) after the temperature and the pressure are increased by a second heater (325).
2. The method for zero-emission treatment of wastewater containing high salt according to claim 1,
and recovering water and salts in the wastewater with high salt content through a wastewater reduction process and an evaporative crystallization process of the concentrated water with high salt content after the wastewater pretreatment process, so as to realize zero emission of the wastewater, wherein the wastewater pretreatment process comprises the steps of adding a flocculation and/or precipitation agent, removing heavy metal ions, hardness ions and organic substances in the wastewater with high salt content through a chemical reactor, and then adjusting the pH value of the wastewater to be alkaline.
3. The method for the zero discharge treatment of wastewater with high salt content according to claim 2, wherein the pretreatment process of the wastewater is completed by the following steps:
the method comprises the steps of homogenizing and uniformly adjusting the wastewater in an adjusting tank (101), sending the wastewater into a high-density tank (102), sequentially adding lime or sodium hydroxide, sodium carbonate, polyaluminium chloride and polyacrylamide into the high-density tank (102) through a dosing device (103), carrying out flocculation and/or precipitation treatment on the wastewater through a chemical reactor, filtering concentrated water generated after treatment through the chemical reactor through a tubular micro-filter (104) and a filter element filter (105), then entering a first intermediate water tank (106), and adjusting the pH value of the wastewater in the first intermediate water tank (106) to be 8.0-9.5.
4. The method for zero discharge treatment of wastewater with high salinity according to claim 3, characterized in that after the sludge generated in the high density pond (102) and the sludge generated in the tubular micro-filter (104) are discharged into a sludge pond (107) and subjected to sludge-water separation by a sludge dewatering device (108), the generated sludge cake is subjected to dry sludge disposal, and the generated water enters the adjusting pond (101) to be mixed with the untreated wastewater for recycling treatment.
5. The method for zero discharge treatment of wastewater with high salt content according to claim 4, wherein the process of wastewater reduction treatment is completed according to the following steps:
the pretreated wastewater collected by the first intermediate water tank (106) is subjected to preliminary reduction treatment by the medium-pressure reverse osmosis device (211) to form medium-pressure reverse osmosis concentrated water and is discharged into the medium-pressure concentrated water tank (212), the medium-pressure reverse osmosis concentrated water collected by the medium-pressure concentrated water tank (212) is further subjected to preliminary reduction treatment by the high-pressure reverse osmosis device (213) to form high-pressure reverse osmosis concentrated water and is discharged into the high-pressure concentrated water tank (214),
and medium-pressure reverse osmosis produced water and high-pressure reverse osmosis produced water formed by the medium-pressure reverse osmosis device (211) and the high-pressure reverse osmosis device (213) enter a reuse water tank (203) after passing through a secondary reverse osmosis device (201) and a fresh water tank (202).
6. The method for zero-emission treatment of wastewater containing high salt according to claim 5,
the high-pressure reverse osmosis concentrated water in the high-pressure concentrated water tank (214) is treated by an activated carbon filter (221) and a resin tank (222) and then discharged into a second intermediate water tank (223) for deep concentration treatment, the high-pressure reverse osmosis concentrated water after pretreatment in the second intermediate water tank (223) enters the second-stage electric-driven ionic membrane device (226) through a first concentrated salt water tank (225) to be further subjected to deep concentration treatment after being treated by the first-stage electric-driven ionic membrane device (224), and is concentrated into high-salt-content concentrated water after being treated by the second-stage electric-driven ionic membrane device (226) and enters a second concentrated salt water tank (227),
the primary electric drive produced water formed after being treated by the primary electric drive ionic membrane device (224) enters the reuse water tank (203) after passing through the secondary reverse osmosis device (201) and the fresh water tank (202).
7. The method for zero discharge treatment of wastewater with high salt content according to claim 6,
the pretreated wastewater in the first intermediate water tank (106) enters a first security filter through a first booster pump, is filtered and then enters the medium-pressure reverse osmosis device (211), and a security filter element of the first security filter is a three-layer stepped filter element, wherein the sizes of the three-layer stepped filter element are respectively 10 micrometers, 15 micrometers and 20 micrometers;
the medium-pressure reverse osmosis concentrated water in the medium-pressure concentrated water tank (212) enters a second cartridge filter through a second booster pump, is filtered and then enters the high-pressure reverse osmosis device (213), and a cartridge filter element of the second cartridge filter is a three-layer stepped filter element, wherein the sizes of the three-layer stepped filter element are respectively 5 micrometers, 10 micrometers and 15 micrometers;
the high-pressure reverse osmosis concentrated water after pretreatment in the second middle water tank (223) enters a third cartridge filter through a third booster pump, is filtered and then enters the first-stage electric-driven ionic membrane device (224), the cartridge filter element of the third cartridge filter is a three-layer stepped filter element, and the sizes of the three-layer stepped filter element are respectively 1 mu m, 5 mu m and 10 mu m.
8. A zero-emission treatment system for high-salt-content wastewater, which comprises a pretreatment process of the wastewater, a reduction process of the wastewater and an evaporative crystallization process of high-salt-content concentrated water, and is characterized in that,
the wastewater reduction process is characterized in that the pretreated wastewater is subjected to preliminary reduction treatment through a medium-pressure reverse osmosis device (211) and a high-pressure reverse osmosis device (213) to form high-pressure reverse osmosis concentrated water, the high-pressure reverse osmosis concentrated water is subjected to deep concentration treatment through a first-stage electric-driven ionic membrane device (224) and a second-stage electric-driven ionic membrane device (226) and then is concentrated into high-salt-content concentrated water, and the wastewater reduction process also recovers water produced in the reduction process to a reuse water tank (203);
the primary electric driven ionic membrane device (224) and the secondary electric driven ionic membrane device (226) comprise an anode and a cathode which are arranged at intervals, a plurality of membrane pairs which are formed by combining a positive membrane, a negative membrane and a partition plate are regularly arranged between the anode and the cathode, the positive membrane and the negative membrane are homogeneous membranes, the partition plate with uniform fluid state is arranged between the two membranes, and the power supply of the primary electric driven ionic membrane device (224) and the secondary electric driven ionic membrane device (226) adopts a high-frequency direct current power supply with positive and negative polarities which are automatically switched and utilizes a digital program to control the power supply, wherein,
the primary electrically-driven ionic membrane device (224) and the secondary electrically-driven ionic membrane device (226) adopt adjustable gap high-frequency oscillation to output high-frequency reversed polarity direct current to disturb a polarizing layer which is easy to form on the surface of the membrane, destroy calcium and magnesium cations with high concentration times in the polarizing layer, and destroy the molecular disproportionation of the polarizing layer in the crystallization process;
the evaporative crystallization process comprises the steps of respectively recovering salts in the high-salt-content concentrated water through a nitrate evaporative crystallization device (302) and a salt evaporative crystallization device (315) under the condition of negative pressure or micro-positive pressure to form sodium sulfate commodity and sodium chloride commodity;
the evaporation crystallization process of the high-salt-content concentrated water is completed according to the following steps:
high-salt-content concentrated water in a second concentrated brine tank (227) is subjected to evaporative crystallization by a nitrate evaporative crystallization device (302) under negative pressure or micro-positive pressure, nitrate mother liquor generated by evaporative crystallization is subjected to freezing crystallization by a freezing nitrate crystallization device (309) and then is subjected to centrifugal separation by a freezing nitrate centrifugal separator (311), decahydrate generated by centrifugation returns to be thermally melted with solid nitrate-containing liquid generated by the nitrate evaporative crystallization device (302), sodium sulfate is separated by the centrifugal separator (304) and then is dried to obtain commercial sodium sulfate,
the frozen nitre mother liquor generated by the centrifugation of the frozen nitre centrifugal separator (311) is evaporated, crystallized and separated out sodium chloride by the salt evaporation crystallization device (315) under negative pressure or micro-positive pressure, and then is dried to obtain commercial sodium chloride, wherein,
after secondary steam generated by evaporation of the saltpeter evaporation crystallization device (302) is compressed and raised in temperature and pressure by a first steam compressor (318), heat energy is continuously provided for high-salt-content concentrated water preheated by a raw material feeding preheater (301) by a first heater (317),
the secondary steam generated by the evaporation of the salt evaporation crystallization device (315) is compressed by a second steam compressor (326) and is used for heating the frozen nitre mother liquor in the heater (314) after the temperature and the pressure are increased by a second heater (325).
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