CN219156728U - High-concentration organic salt water treatment system - Google Patents

Abstract

The utility model discloses a high-concentration organic brine treatment system which comprises a pretreatment system and a deep treatment system, wherein the pretreatment system comprises a concentrated brine regulating tank, a first pretreatment unit, a first-stage reverse osmosis device, a second pretreatment unit, a second-stage reverse osmosis device and a pretreatment liquid regulating tank; the advanced treatment system comprises a nanofiltration treatment unit, an ozone catalytic oxidation unit, an organic concentration unit, a sodium chloride crystallization unit, a sodium sulfate crystallization unit and a salt mixing treatment unit. The high-concentration organic salt water is treated by a pretreatment system and an advanced treatment system, and the crystalline salt and the reuse water which meet the industrial standard are recovered, so that the foreign salt discharge is reduced.

Description

High-concentration organic salt water treatment system

Technical field:

the utility model relates to the technical field of salt-containing wastewater treatment, in particular to a high-concentration organic salt water treatment system.

The background technology is as follows:

the high-concentration salt-containing wastewater mainly comes from the production process of petrochemical industry and coal chemical industry enterprises, the wastewater has complex water quality and high pollutant concentration, contains a large amount of solid suspended matters, has various nondegradable pollutant types and complex structures, such as various phenols, cyanides, polycyclic aromatic hydrocarbons, thiocyanides, benzopyrene, quinoline, indole, biphenyl, oil and the like, also contains various inorganic pollutants such as ammonia nitrogen, sulfide and the like, has high COD (chemical oxygen demand) and chromaticity, and belongs to industrial wastewater which is difficult to treat. In addition, the waste water has great harm and poor biodegradability, wherein various organic pollutants such as heterocycle and aromatic hydrocarbon compounds have high content and are difficult to biodegrade, cyanide belongs to highly toxic substances, phenol belongs to highly toxic substances and has toxic action on organisms; the ammonia nitrogen concentration of the wastewater is high, and the biodegradability is poor.

The conventional salt-containing wastewater evaporation process is to evaporate and crystallize salt-containing wastewater, then centrifuge to obtain crystallized salt, discharge the crystallized supernatant and the centrifuged supernatant into a mother liquid tank, and send one part back to the evaporator for continuous use and the other part directly discharge the other part for other treatments. However, the high-concentration organic brine contains a large amount of viscous undegradable macromolecular organic matters, polymers and unidentified substances, and has the advantages of large molecular weight, high boiling point and high viscosity, and when the high-concentration organic brine enters an evaporation system, the substances are greatly enriched along with evaporation and concentration, so that the viscosity of the solution is improved, and the following problems are caused: (1) The evaporation boiling point is increased, the coking carbonization, the scaling blockage and the evaporation capacity of the organic matters are obviously reduced; (2) The salt is wrapped by the organic matters, so that lattice distortion is caused, the salt is not easy to crystallize and grow, fine salt is increased, and the concentration and viscosity of the solution are further increased due to non-crystallized malformed salt; (3) Organic matters are not effectively treated, so that the foaming of the crystallizer is serious, and the quality of condensed water and the stability of a system are affected; (4) Part of the sticky matters are wrapped in the crystal salt in a surface adhesion or inter-crystal occlusion mode and are discharged together with the crystal salt, so that the impurity content of the crystal salt is increased, the crystal salt is sticky, the color is deep, the water content is high, and the quality is obviously reduced; (5) The desalted mother liquid contains a large amount of organic matters and fine salt wrapped by the organic matters, so that a large amount of energy is consumed in the subsequent treatment, and a large amount of hazardous waste is generated.

Therefore, a treatment system for high-concentration organic brine needs to be designed, and divalent ions, small-molecule organic matters, undegraded macromolecule organic matters, polymers, unidentified matters and the like in the high-concentration organic brine are treated to obtain high-quality sodium chloride and sodium sulfate.

The utility model comprises the following steps:

the utility model aims to provide a high-concentration organic brine treatment system which is used for effectively treating high-concentration organic brine, recovering crystalline salt and reuse water meeting industrial standards, reducing impurity salt discharge and saving energy consumption.

The utility model is implemented by the following technical scheme:

the pretreatment system comprises a concentrated brine regulating tank, a first pretreatment unit, a first reverse osmosis device, a second pretreatment unit, a second reverse osmosis device and a pretreatment liquid regulating tank; the advanced treatment system comprises a nanofiltration treatment unit, an ozone catalytic oxidation unit, an organic concentration unit, a sodium chloride crystallization unit, a sodium sulfate crystallization unit and a salt mixing treatment unit; the strong brine outlet of the strong brine regulating tank is communicated with the strong brine inlet of the first pretreatment unit; the treatment liquid outlet of the first pretreatment unit is communicated with the liquid inlet of the first-stage reverse osmosis device; the concentrated water outlet of the first-stage reverse osmosis device is communicated with the liquid inlet of the second pretreatment unit; the treatment liquid outlet of the second pretreatment unit is communicated with the liquid inlet of the secondary reverse osmosis device; the concentrated water outlet of the secondary reverse osmosis device is communicated with the liquid inlet of the pretreatment liquid regulating tank; the liquid outlet of the pretreatment liquid adjusting tank is communicated with the liquid inlet of the nanofiltration treatment unit; the nanofiltration water outlet of the nanofiltration treatment unit is communicated with the liquid inlet of the ozone catalytic oxidation unit, and the nanofiltration concentrated water outlet of the nanofiltration treatment unit is communicated with the liquid inlet of the organic concentration unit; the treatment liquid outlet of the ozone catalytic oxidation unit is communicated with the liquid inlet of the sodium chloride crystallization unit; the concentrated solution outlet of the organic concentration unit is communicated with the liquid inlet of the sodium sulfate crystallization unit; the mother liquor outlet of the sodium chloride crystallization unit is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit, and the mother liquor outlet of the organic concentration unit is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit; and a filtrate outlet of the salt mixing treatment unit is communicated with a liquid inlet of the nanofiltration treatment unit. And sequentially treating the high-concentration organic salt water to be treated, backwash water, resin regenerated water and sludge filtrate generated in the process by the pretreatment system and the advanced treatment system, basically removing divalent ions, organic matters and other impurities in the solution to be treated to obtain high-quality sodium chloride crystal salt, sodium sulfate crystal salt, and carrying out other treatments on mixed salt and impurity salt.

Further, the first pretreatment unit comprises a two-stage softening and desilication high-density tank, a first-stage sand filtration tank, a first-stage ultrafiltration device and a resin softening device which are sequentially communicated; the two-stage softening and desilication high-density tank comprises a first-stage softening tank, a first-stage sedimentation tank, a second-stage desilication tank and a second-stage sedimentation tank which are sequentially communicated; the concentrated brine inlet of the primary softening tank is communicated with the concentrated brine outlet of the concentrated brine regulating tank; the liquid outlet of the secondary sedimentation tank is communicated with the liquid inlet of the primary sand filtration tank; the treatment fluid outlet of the resin softening device is communicated with the fluid inlet of the first-stage reverse osmosis device. After the liquid to be treated enters the strong brine regulating tank for homogenizing and homogenizing, part of suspended solids and divalent ions such as calcium, magnesium, silicon and the like in the liquid to be treated are removed through the two-stage softening and desilication high-density tank, suspended matters in the liquid to be treated are removed through sand filtration and ultrafiltration, the turbidity of the liquid is reduced, and deep softening is carried out through a resin softening device.

Further, the second pretreatment unit comprises a decarburization tower, a decarburization water producing tank, a desilication high-density tank, a second sand filtration tank and a second ultrafiltration device which are sequentially communicated; the silicon-removing high-density tank comprises a three-stage silicon-removing tank and a three-stage sedimentation tank which are sequentially communicated; the liquid inlet of the decarburization tower is communicated with the concentrated water outlet of the primary reverse osmosis device; the liquid inlet of the three-stage silicon removal pool is communicated with the liquid outlet of the decarburization water producing pool; the liquid outlet of the third-stage sedimentation tank is communicated with the liquid inlet of the second-stage sand filter tank; the treatment fluid outlet of the secondary ultrafiltration device is communicated with the fluid inlet of the secondary reverse osmosis device. And (3) removing carbonate ions in the liquid by the concentrated water concentrated by the primary reverse osmosis device through the decarbonization tower, reducing the alkalinity of the liquid, enabling the decarbonized produced water to enter the decarbonized water producing pool for homogenization adjustment, and then basically removing divalent ions, suspended matters and other impurities after the concentrated water is treated by the silicon removing high-density pool, the secondary sand filter tank and the secondary ultrafiltration device.

Further, the pretreatment system also comprises a sludge treatment system; the sludge outlet of the primary sedimentation tank is communicated with the sludge inlet of the sludge treatment system; the sludge outlet of the secondary sedimentation tank is communicated with the sludge inlet of the sludge treatment system; and a sludge outlet of the three-stage sedimentation tank is communicated with a sludge inlet of the sludge treatment system. The water-containing sludge generated by the primary sedimentation tank and the secondary sedimentation tank of the two-stage softening and desilication high-density tank is conveyed to the sludge treatment system, and the water-containing sludge generated by the tertiary sedimentation tank of the desilication high-density tank is conveyed to the sludge treatment system for treatment and outward transportation treatment.

Further, the pretreatment system also comprises a deamination resin tank, a pure water reverse osmosis device and a reverse osmosis water producing tank; the evaporation condensate water outlet of the sodium chloride crystallization unit is communicated with the liquid inlet of the deamination resin tank; the liquid outlet of the deamination resin tank is communicated with the liquid inlet of the pure water reverse osmosis device; the water outlet of the secondary reverse osmosis device is communicated with the liquid inlet of the pure water reverse osmosis device; the concentrated water outlet of the pure water reverse osmosis device is communicated with the liquid inlet of the primary reverse osmosis device; the water outlet of the pure water reverse osmosis device is communicated with the liquid inlet of the reverse osmosis water producing tank; the liquid inlet of the reverse osmosis water producing pool is communicated with the water producing outlet of the first-stage reverse osmosis device. And introducing evaporation condensate water in the sodium chloride crystallization device into the deamination resin tank for deamination, and then performing reverse osmosis through the pure water reverse osmosis device, wherein after the pure water reverse osmosis device performs reverse osmosis on the evaporation condensate water after deamination and produced water of the secondary reverse osmosis device, produced water is introduced into the reverse osmosis water producing pool for recycling, and concentrated water is introduced into the primary reverse osmosis device for reprocessing.

Further, the nanofiltration treatment unit comprises a first security filter and at least two stages of nanofiltration membrane devices which are sequentially communicated; the liquid inlet of the first security filter is communicated with the liquid outlet of the pretreatment liquid adjusting tank; the nanofiltration water outlet of the nanofiltration membrane device is communicated with the liquid inlet of the ozone catalytic oxidation unit, and the nanofiltration concentrated water outlet of the nanofiltration membrane device is communicated with the liquid inlet of the organic concentration unit. After pretreatment by the pretreatment system, the concentrated water subjected to reverse osmosis by the secondary reverse osmosis device is homogenized in the pretreatment liquid regulating tank, and is introduced into the nanofiltration treatment unit for treatment, so that the functions of separating salt and separating organic matters are realized, divalent ions can be trapped, and nanofiltration produced water rich in sodium chloride and nanofiltration concentrated water rich in sodium sulfate are obtained; in addition, the nanofiltration treatment unit also has partial interception and screening effects on organic matters, wherein macromolecular organic matters are intercepted to a nanofiltration concentrate side, enter the organic concentration unit for treatment, and small-molecular and easily-degradable organic matters are intercepted to a nanofiltration product side and enter the ozone catalytic oxidation unit for treatment.

Further, the ozone catalytic oxidation unit comprises an ozone generator, a catalytic oxidation reaction device and a tail gas collecting device which are sequentially communicated; the liquid inlet of the catalytic oxidation reaction device is communicated with the nanofiltration water outlet of the nanofiltration membrane device; and a treatment fluid outlet of the catalytic oxidation reaction device is communicated with a fluid inlet of the sodium chloride crystallization unit. The ozone produced by the ozone generator reacts with nanofiltration produced water in the catalytic oxidation reaction device, the produced tail gas is collected and treated by the tail gas collecting device, and micromolecular organic matters in the nanofiltration produced water are basically removed.

Further, the sodium chloride crystallization unit comprises a sodium chloride evaporation raw water tank, an MVR falling film concentration device, an MVR evaporation crystallization device, a sodium chloride thickener, a sodium chloride centrifuge, a sodium chloride drying bed and a sodium chloride packaging machine which are sequentially communicated; the liquid inlet of the sodium chloride evaporation raw water tank is communicated with the treatment liquid outlet of the catalytic oxidation reaction device; the crystal slurry outlet of the MVR evaporation crystallization device is communicated with the liquid inlet of the sodium chloride thickener; the mother liquor outlet of the MVR evaporation crystallization device is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit; and an evaporation condensate outlet of the MVR evaporation crystallization device is communicated with a liquid inlet of the deamination resin tank. The nanofiltration produced water enters the sodium chloride crystallization unit after ozone catalytic oxidation reaction, and is regulated and homogenized by the sodium chloride evaporation raw water tank, so that the stability of the quality and the quantity of water in the sodium chloride crystallization process is ensured; the MVR falling film is used for primarily concentrating the produced water in the sodium chloride evaporation raw water tank, so that the scale of a subsequent evaporation system can be effectively reduced, and the overall investment cost is reduced; then sending the sodium chloride crystal slurry obtained by MVR evaporation crystallization into the sodium chloride thickener for thickening, so that the particles of the crystal salt can be increased, and the crystal salt in the crystal slurry can be separated from the mother liquor, so that the water content in the crystal salt is reduced, and the volume of centrifugal equipment is further reduced; and then carrying out centrifugal solid-liquid separation on the thickened crystal slurry, drying the obtained sodium chloride crystal salt, and packaging to obtain the high-quality sodium chloride crystal salt.

Further, the organic concentration unit comprises a second cartridge filter and an organic film concentration device which are sequentially communicated; the liquid inlet of the second security filter is communicated with the nanofiltration concentrated water outlet of the nanofiltration membrane device; the concentrated solution outlet of the organic film concentration device is communicated with the liquid inlet of the sodium sulfate crystallization unit; and a mother liquor outlet of the organic film concentration device is communicated with a mixed salt mother liquor inlet of the mixed salt treatment unit. The nanofiltration concentrated water is filtered and concentrated by an organic film, so that macromolecule and nondegradable waste organic matters can be intercepted, the concentrated solution enters the sodium sulfate crystallization unit for the next process, and the mother solution enters the salt mixing treatment unit for treatment, thereby avoiding the pollution of direct discharge to the environment.

Further, the sodium sulfate crystallization unit comprises a sodium sulfate evaporation raw water tank, a freezing feeding tank, a freezing crystallization device, a primary sodium sulfate thickener, a primary sodium sulfate centrifuge, a hot melt crystallization device, a secondary sodium sulfate thickener, a secondary sodium sulfate centrifuge, a sodium sulfate drying bed and a sodium sulfate packaging machine which are sequentially communicated; the liquid inlet of the sodium sulfate evaporation raw water tank is communicated with the concentrated liquid outlet of the organic film concentrating device; the crystal slurry outlet of the freezing crystallization device is communicated with the liquid inlet of the primary sodium sulfate thickener, and the mother liquor outlet of the freezing crystallization device is communicated with the liquid inlet of the first security filter. Concentrating nanofiltration concentrated water through an organic film, and then entering the sodium sulfate crystallization unit; the raw water pool evaporated by sodium sulfate is regulated and homogenized, so that the stability of the quality and the quantity of water in the crystallization process of sodium sulfate is ensured; the concentrated water in the sodium sulfate evaporation raw water tank is introduced into the freezing feeding tank for preliminary precooling, so that the time of subsequent freezing and crystallization can be effectively shortened, and the cost is reduced; freezing and crystallizing concentrated water in the freezing and crystallizing device, sequentially thickening and centrifuging the obtained mirabilite slurry by the primary sodium sulfate thickener and the primary sodium sulfate centrifuge, sending the concentrated water into the hot-melt crystallizing device to obtain sodium sulfate crystal slurry with higher purity, concentrating and drying sodium sulfate crystal salt by the processes of thickening, centrifuging, drying and the like, and packaging to obtain high-quality sodium sulfate crystal salt; and (3) enabling the crystal slurry processed by the freezing crystallization device to enter the sodium sulfate thickener for thickening, and introducing mother liquor into the nanofiltration treatment unit for reprocessing.

Further, the salt mixing treatment unit comprises a salt mixing evaporation crystallization device, a salt mixing thickener, a salt mixing centrifuge, a roller dryer, a high-temperature incinerator, a salt dissolving system and a deslagging system which are sequentially communicated; the mixed salt mother liquor inlet of the mixed salt evaporation crystallization device is communicated with the mother liquor outlet of the MVR evaporation crystallization device; the mixed salt mother liquor inlet of the roller dryer is communicated with the mother liquor outlet of the organic film concentration device; and a filtrate outlet of the deslagging system is communicated with a liquid inlet of the first security filter. Sodium sulfate in mother liquor discharged from the MVR evaporation crystallization device is nearly saturated, the mother liquor enters the mixed salt evaporation crystallization device for further treatment, and the mixed salt obtained after thickening and centrifugation is dissolved back into a sodium sulfate raw water tank; drying the centrifuged mixed salt mother liquor and the organic concentrated mother liquor of the organic film concentrating device by the roller dryer to obtain mixed salt containing sodium chloride, sodium sulfate, organic matters and the like; the traditional disc is easy to harden, has high water content, needs to be cleaned manually for many times, uses a roller dryer to treat the salt-containing mother liquor, and has high heat efficiency and high drying rate; the mixed salt is burnt in the high-temperature incinerator at 300-600 ℃, and organic matters contained in the mixed salt are carbonized, and salts such as sodium chloride, sodium sulfate and the like are reserved; dissolving carbonized mixed salt in water through the salt dissolving system, dissolving sodium chloride and sodium sulfate in liquid, filtering through the deslagging system, discharging filter residues, namely carbonized organic matters, serving as common solid waste treatment, and introducing filtrate containing sodium chloride and sodium sulfate into the nanofiltration treatment unit for reprocessing. Mother liquor generated in the crystallization process of sodium chloride and the organic concentration process of nanofiltration concentrated water is treated by the mixed salt treatment unit, the obtained mixed salt is dissolved back, organic matters in the mixed salt are carbonized and filtered to be used as solid waste treatment, and filtrate containing sodium chloride and sodium sulfate is recycled, so that the discharge of the mixed salt is reduced.

The utility model has the advantages that:

and (3) treating the high-concentration organic brine by a pretreatment system and an advanced treatment system to obtain high-quality sodium chloride and sodium sulfate. After impurities such as divalent ions such as calcium, magnesium and silicon, suspended matters and carbonate ions in high-concentration organic salt water are basically removed through processes such as silicon removal, decarburization, filtration, softening, reverse osmosis and the like, separating the salt and separating the organic matters through a nanofiltration treatment unit to obtain nanofiltration produced water with high content of micromolecular organic matters and nanofiltration concentrated water with high content of macromolecule refractory organic matters, and preparing the high-quality sodium chloride crystal salt through processes such as ozone catalytic oxidation, falling film concentration, evaporative crystallization, thickening centrifugation and the like; the nanofiltration concentrated water is subjected to organic concentration, freezing crystallization, hot melt crystallization, thickening centrifugation and other processes to prepare the high-quality sodium sulfate crystal salt.

Mother liquor generated in the crystallization process of sodium chloride and the organic concentration process of nanofiltration concentrated water is treated by a mixed salt treatment unit, the obtained mixed salt is dissolved back, and organic matters in the mixed salt are carbonized and filtered to be used as solid waste treatment and filtrate containing sodium chloride and sodium sulfate for recycling; the water-containing sludge generated in the pretreatment process is conveyed to the sludge treatment system for treatment and then is transported outwards; the evaporated condensate water and the reverse osmosis concentrated water generated in the treatment process are recycled or reprocessed after reverse osmosis by a pure water reverse osmosis device. The system effectively treats the high-concentration organic salt water, recovers the crystalline salt and the reuse water which meet the industrial standard, and reduces the foreign salt discharge.

Description of the drawings:

in order to more clearly illustrate the embodiments of the utility model or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the utility model, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a schematic diagram of a high concentration organic brine treatment system;

FIG. 2 is a schematic diagram of a pretreatment system of a high concentration organic brine treatment system;

FIG. 3 is a schematic diagram of an advanced treatment system of a high concentration organic brine treatment system.

The drawings are as follows:

1. a strong brine adjusting tank; 11. a first preprocessing unit; 111. two-stage softening and desilication high-density tanks; 112. a first-stage sand filter tank; 113. a primary ultrafiltration device; 114. a resin softening device; 12. a first stage reverse osmosis unit; 13. a second pretreatment unit; 131. a decarburization tower; 132. decarburizing a water producing tank; 133. removing silicon from the high-density pool; 134. a second stage sand filtration tank; 135. a secondary ultrafiltration device; 14. a secondary reverse osmosis device; 15. a sludge treatment system; 16. a deamination resin tank; 17. a pure water reverse osmosis device; 18. a reverse osmosis water producing pool;

2. a pretreatment liquid adjusting tank; 21. a nanofiltration treatment unit; 211. a first security filter; 212. nanofiltration membrane device; 22. an ozone catalytic oxidation unit; 221. an ozone generator; 222. a catalytic oxidation reaction device; 223. a tail gas collection device; 23. a sodium chloride crystallization unit; 230. sodium chloride evaporation raw water pool; 231. MVR falling film concentration device; 232. MVR evaporation crystallization device; 233. sodium chloride thickener; 234. a sodium chloride centrifuge; 235. sodium chloride dry bed; 236. sodium chloride packing machine; A. sodium chloride crystalline salt; 24. an organic concentration unit; 241. a second cartridge filter; 242. an organic film concentrating device; 25. a sodium sulfate crystallization unit; 250. evaporating a raw water pool by sodium sulfate; 251. freezing the feed tank; 252. a freeze crystallization device; 253. a primary sodium sulfate thickener; 254. a primary sodium sulfate centrifuge; 255. a hot melt crystallization device; 256. a second-stage sodium sulfate thickener; 257. a secondary sodium sulfate centrifuge; 258. a sodium sulfate dry bed; 259. sodium sulfate packaging machine; 26. a salt mixing treatment unit; 261. a salt mixing evaporation crystallization device; 262. a salt mixing thickener; 263. salt mixing centrifugal machine; 264. a drum dryer; 265. a high temperature incinerator; 266. a salt dissolving system; 267. a deslagging system; B. sodium sulfate crystalline salt.

The specific embodiment is as follows:

the following description of the embodiments of the present utility model will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present utility model, but not all embodiments. In the description of the present utility model, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present utility model and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present utility model. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model.

Examples

A high-concentration organic brine treatment system, as shown in fig. 1, comprises a pretreatment system and a deep treatment system, wherein the pretreatment system comprises a concentrated brine regulating tank 1, a first pretreatment unit 11, a first reverse osmosis device 12, a second pretreatment unit 13, a second reverse osmosis device 14 and a pretreatment liquid regulating tank 2; the advanced treatment system comprises a nanofiltration treatment unit 21, an ozone catalytic oxidation unit 22, a sodium chloride crystallization unit 23, an organic concentration unit 24, a sodium sulfate crystallization unit 25 and a salt mixing treatment unit 26; the strong brine outlet of the strong brine regulating tank 1 is communicated with the strong brine inlet of the first pretreatment unit 11; the treatment liquid outlet of the first pretreatment unit 11 is communicated with the liquid inlet of the first-stage reverse osmosis device 12; the concentrated water outlet of the first-stage reverse osmosis device 12 is communicated with the liquid inlet of the second pretreatment unit 13; the treatment fluid outlet of the second pretreatment unit 13 is communicated with the fluid inlet of the secondary reverse osmosis device 14; the concentrated water outlet of the secondary reverse osmosis device 14 is communicated with the liquid inlet of the pretreatment liquid adjusting tank 2; the liquid outlet of the pretreatment liquid adjusting tank 2 is communicated with the liquid inlet of the nanofiltration treatment unit 21; the nanofiltration water outlet of the nanofiltration treatment unit 21 is communicated with the liquid inlet of the ozone catalytic oxidation unit 22, and the nanofiltration concentrated water outlet of the nanofiltration treatment unit 21 is communicated with the liquid inlet of the organic concentration unit 24; the treatment liquid outlet of the ozone catalytic oxidation unit 22 is communicated with the liquid inlet of the sodium chloride crystallization unit 23; the concentrated solution outlet of the organic concentration unit 24 is communicated with the liquid inlet of the sodium sulfate crystallization unit 25; the mother liquor outlet of the sodium chloride crystallization unit 23 is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit 26, and the mother liquor outlet of the organic concentration unit 24 is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit 26; the filtrate outlet of the salt mixing treatment unit 26 is communicated with the liquid inlet of the nanofiltration treatment unit 21.

As shown in fig. 2, the first pretreatment unit 11 includes a two-stage softening and desilication high-density tank 111, a first-stage sand filtration tank 112, a first-stage ultrafiltration device 113, and a resin softening device 114, which are sequentially communicated; the two-stage softening and desilication high-density tank 111 comprises a first-stage softening tank, a first-stage sedimentation tank, a second-stage desilication tank and a second-stage sedimentation tank which are sequentially communicated; the concentrated brine inlet of the primary softening tank is communicated with the concentrated brine outlet of the concentrated brine regulating tank 1; the liquid outlet of the secondary sedimentation tank is communicated with the liquid inlet of the primary sand filtration tank 112; the treatment fluid outlet of the resin softening unit 114 communicates with the inlet of the primary reverse osmosis unit 12.

The second pretreatment unit 13 comprises a decarburization tower 131, a decarburization water producing pool 132, a desilication high-density pool 133, a secondary sand filter tank 134 and a secondary ultrafiltration device 135 which are sequentially communicated; the desilication high-density tank 133 comprises a three-stage desilication tank and a three-stage sedimentation tank which are communicated in sequence; the liquid inlet of the decarburization tower 131 is communicated with the concentrated water outlet of the primary reverse osmosis device 12; the liquid inlet of the three-stage desilication pool is communicated with the liquid outlet of the decarburization water producing pool 132; the liquid outlet of the third-stage sedimentation tank is communicated with the liquid inlet of the second-stage sand filter tank 134; the treatment fluid outlet of the secondary ultrafiltration device 135 communicates with the inlet of the secondary reverse osmosis device 14.

The pretreatment system further comprises a sludge treatment system 15; the sludge outlet of the primary sedimentation tank is communicated with the sludge inlet of the sludge treatment system 15; the sludge outlet of the secondary sedimentation tank is communicated with the sludge inlet of the sludge treatment system 15; the sludge outlet of the three-stage sedimentation tank is communicated with the sludge inlet of the sludge treatment system 15.

The pretreatment system also comprises a deamination resin tank 16, a pure water reverse osmosis device 17 and a reverse osmosis water producing tank 18; the evaporation condensate outlet of the sodium chloride crystallization unit 23 is communicated with the liquid inlet of the deamination resin tank 16; the liquid outlet of the deamination resin tank 16 is communicated with the liquid inlet of the pure water reverse osmosis device 17; the water outlet of the secondary reverse osmosis device 14 is communicated with the liquid inlet of the pure water reverse osmosis device 17; the concentrated water outlet of the pure water reverse osmosis device 17 is communicated with the liquid inlet of the primary reverse osmosis device 12; the water outlet of the pure water reverse osmosis device 17 is communicated with the liquid inlet of the reverse osmosis water producing tank 18; the liquid inlet of the reverse osmosis water producing tank 18 is communicated with the water producing outlet of the first-stage reverse osmosis device 12.

As shown in fig. 3, the nanofiltration treatment unit 21 includes a first security filter 211 and a two-stage nanofiltration membrane device 212 which are sequentially connected; the liquid inlet of the first security filter 211 is communicated with the liquid outlet of the pretreatment liquid adjusting tank 2; the nanofiltration water outlet of the nanofiltration membrane device 212 is communicated with the liquid inlet of the ozone catalytic oxidation unit 22, and the nanofiltration concentrated water outlet of the nanofiltration membrane device 212 is communicated with the liquid inlet of the organic concentration unit 24.

The ozone catalytic oxidation unit 22 comprises an ozone generator 221, a catalytic oxidation reaction device 222 and a tail gas collecting device 223 which are sequentially communicated; the liquid inlet of the catalytic oxidation reaction device 222 is communicated with the nanofiltration water outlet of the nanofiltration membrane device 212; the treatment liquid outlet of the catalytic oxidation reaction device 222 is communicated with the liquid inlet of the sodium chloride crystallization unit 23.

The sodium chloride crystallization unit 23 comprises a sodium chloride evaporation raw water tank 230, an MVR falling film concentration device 231, an MVR evaporation crystallization device 232, a sodium chloride thickener 233, a sodium chloride centrifuge 234, a sodium chloride drying bed 235 and a sodium chloride packing machine 236 which are sequentially communicated; the liquid inlet of the sodium chloride evaporation raw water tank 230 is communicated with the treatment liquid outlet of the catalytic oxidation reaction device 222; the crystal slurry outlet of the MVR evaporation crystallization device 232 is communicated with the liquid inlet of the sodium chloride thickener 233; the mother liquor outlet of the MVR evaporation crystallization device 232 is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit 26; the vapor condensate outlet of the MVR vapor crystallization device 232 communicates with the liquid inlet of the deamination resin tank 16.

The organic concentration unit 24 includes a second cartridge filter 241 and an organic film concentration device 242 which are sequentially communicated; the liquid inlet of the second cartridge filter 241 is communicated with the nanofiltration concentrated water outlet of the nanofiltration membrane device 212; the concentrated solution outlet of the organic film concentrating device 242 is communicated with the liquid inlet of the sodium sulfate crystallization unit 25; the mother liquor outlet of the organic film concentrating device 242 is in communication with the mixed salt mother liquor inlet of the mixed salt treatment unit 26.

The sodium sulfate crystallization unit 25 comprises a sodium sulfate evaporation raw water tank 250, a freezing feed tank 251, a freezing crystallization device 252, a primary sodium sulfate thickener 253, a primary sodium sulfate centrifuge 254, a hot melt crystallization device 255, a secondary sodium sulfate thickener 256, a secondary sodium sulfate centrifuge 257, a sodium sulfate dry bed 258 and a sodium sulfate packaging machine 259 which are sequentially communicated; the liquid inlet of the sodium sulfate evaporation raw water tank 250 is communicated with the concentrated liquid outlet of the organic film concentration device 242; the crystal slurry outlet of the freezing and crystallizing device 252 is communicated with the liquid inlet of the primary sodium sulfate thickener 253, and the mother liquor outlet of the freezing and crystallizing device 252 is communicated with the liquid inlet of the first security filter 211.

The salt mixing treatment unit 26 comprises a salt mixing evaporation crystallization device 261, a salt mixing thickener 262, a salt mixing centrifuge 263, a roller dryer 264, a high-temperature incinerator 265, a salt dissolving system 266 and a deslagging system 267 which are sequentially communicated; the mixed salt mother liquor inlet of the mixed salt evaporation crystallization device 261 is communicated with the mother liquor outlet of the MVR evaporation crystallization device 232; the impurity salt mother liquor inlet of the roller dryer 264 is communicated with the mother liquor outlet of the organic film concentration device 242; the filtrate outlet of the deslagging system 267 is in communication with the liquid inlet of the first safety filter 211.

When the high-concentration organic brine treatment system is operated, the concentrated brine is introduced into a concentrated brine regulating tank 1, and backwash water, resin regenerated water, sludge filtrate and the like generated in other working procedures can also be introduced into the concentrated brine regulating tank 1 for homogenization and regulation, and then introduced into a one-stage softening tank of a two-stage softening and desilication high-concentration tank 111; lime, sodium carbonate, PFS and PAM are added into a reaction lattice of the primary softening tank for reaction, then the primary sedimentation tank is used for sedimentation, the precipitated water-containing sludge is conveyed to a sludge treatment system 15 for treatment, the supernatant fluid after sedimentation is introduced into a secondary desilication tank, magnesium agent, PFS and PAM are added into the reaction lattice of the secondary desilication tank for reaction, then the secondary sedimentation tank is used for sedimentation, the precipitated water-containing sludge is conveyed to the sludge treatment system 15 for treatment, and part of calcium, magnesium, silicon ions and suspended solids in the supernatant fluid after sedimentation are removed; the supernatant fluid after softening and desilication in the two-stage softening and desilication high-density tank 111 is filtered by a first-stage sand filter tank 112 and a first-stage ultrafiltration device 113 in sequence, so that suspended matters in the supernatant fluid are removed, and the turbidity of the liquid is reduced; then the resin is introduced into a resin softening device 114 for deep softening; the softened liquid enters a first-stage reverse osmosis device 12 for concentration, concentrated water after concentration enters a decarburization tower 131 of a second pretreatment unit 13, and produced water enters a reverse osmosis water producing tank 18; the concentrated water is subjected to removal of carbonate ions in the concentrated water through a decarbonization tower 131, the alkalinity is reduced, then the concentrated water is introduced into a decarbonization water producing pool 132 for homogenization adjustment, and then enters a desilication high-density pool 133, hydrochloric acid, desilication agent, PFS and PAM are added into reaction grids of a three-stage desilication pool for reaction, then the concentrated water is subjected to precipitation in a three-stage precipitation pool, the precipitated aqueous sludge is conveyed to a sludge treatment system 15 for treatment, and calcium, magnesium, silicon ions and suspended solids in supernatant liquid after precipitation are basically removed; the supernatant fluid softened and removed by the silicon removing high-density tank 133 is filtered by a second-stage sand filter tank 134 and a second-stage ultrafiltration device 135 in sequence, so that suspended matters in the supernatant fluid are basically removed, and the turbidity of the liquid is reduced; and then enters a secondary reverse osmosis device 14 for concentration, and concentrated water after concentration enters a pretreatment liquid regulating tank 2.

The concentrated water enters a nanofiltration treatment unit 21 after being regulated and homogenized by a pretreatment liquid regulating tank 2, enters a nanofiltration membrane device 212 after being filtered by a first security filter 211 to separate salt and organic matters, divalent ions are trapped, the organic matters are partially trapped and screened, and nanofiltration product water rich in sodium chloride containing small molecules and degradable organic matters and nanofiltration concentrate water rich in sodium sulfate containing macromolecular organic matters are obtained, and the nanofiltration product water enters an ozone catalytic oxidation unit 22 to be treated, and the nanofiltration concentrate water enters an organic concentration unit 24 to be treated.

After the nanofiltration product water is subjected to ozone catalytic oxidation reaction with ozone from an ozone generator 221 in a catalytic oxidation reaction device 222, micromolecule and easily degradable organic matters in the nanofiltration product water are efficiently removed, tail gas is led into a tail gas collecting device 223, and the treated nanofiltration product water enters a sodium chloride crystallization unit 23; after being regulated and homogenized by the sodium chloride evaporation raw water tank 230, the nanofiltration produced water is primarily concentrated by the MVR falling film concentration device 231, so that the scale of a subsequent evaporation system is effectively reduced, and the overall investment cost is reduced; then the nanofiltration produced water after the falling film concentration is evaporated and crystallized through an MVR evaporation crystallization device 232, the evaporated condensate water after the evaporation and crystallization is led into a deamination resin tank 16 for deamination and then is subjected to reverse osmosis through a pure water reverse osmosis device 17, the pure water reverse osmosis device 17 carries out reverse osmosis on the evaporated condensate water after the deamination and the produced water of a secondary reverse osmosis device 14, and then the produced water is led into a reverse osmosis produced water tank 18 for recycling, and the concentrated water is led into a primary reverse osmosis device 12 for reprocessing; the sodium chloride crystal slurry obtained by evaporation and crystallization is sent to a sodium chloride thickener 233 for thickening, so that the particles of the crystal salt are increased, the crystal salt in the crystal slurry is separated from the mother liquor, the water content in the crystal salt is reduced, and the volume of centrifugal equipment is further reduced; and centrifuging the thickened crystal slurry in a sodium chloride centrifuge 234, performing solid-liquid separation, drying the obtained sodium chloride crystal salt through a sodium chloride drying bed 235 and a sodium chloride packaging machine 236, and packaging to obtain high-quality sodium chloride crystal salt A.

The nanofiltration concentrated water is filtered by the second cartridge filter 241 and then enters the organic film concentration device 242, macromolecule and nondegradable waste organic matters can be intercepted, the concentrated solution enters the sodium sulfate crystallization unit 25 for the next procedure, and the mother solution enters the salt mixing treatment unit 26 for treatment, so that the pollution of direct discharge to the environment is avoided. The concentrated water treated by the organic film concentration device 242 is adjusted and homogenized by the sodium sulfate evaporation raw water tank 250 and then is introduced into the freezing feed tank 251 for preliminary precooling, so that the time of subsequent freezing crystallization can be effectively shortened, and the cost is reduced; freezing and crystallizing the concentrated water in a freezing and crystallizing device 252, introducing the mother liquor into a nanofiltration treatment unit 21 for reprocessing, sequentially passing the obtained mirabilite slurry through a primary sodium sulfate thickener 253 and a primary sodium sulfate centrifuge 254 for thickening and centrifuging, and then introducing the concentrated water into a hot-melt crystallizing device 255 to obtain sodium sulfate crystal slurry with higher purity; and (3) carrying out thickening and centrifugation on the crystal slurry obtained by hot-melt crystallization sequentially through a secondary sodium sulfate thickener 256 and a secondary sodium sulfate centrifuge 257, carrying out solid-liquid separation, drying the obtained sodium sulfate crystal salt through a sodium sulfate drying bed 258 and a sodium sulfate packaging machine 259, and packaging to obtain high-quality sodium sulfate crystal salt B.

Sodium sulfate in mother liquor discharged by the MVR evaporation crystallization device 232 is nearly saturated, the mother liquor enters a mixed salt evaporation crystallization device 261 for evaporation crystallization, mixed salt crystal slurry is sequentially fed into a mixed salt thickener 262 and a mixed salt centrifuge 263 for thickening and centrifuging, the centrifuged mixed salt is dissolved back into a sodium sulfate raw water pool, the impurity salt amount is reduced, the treatment cost is reduced, the centrifuged mixed salt mother liquor and organic concentrated mother liquor discharged by an organic film concentration device 242 are dried in a roller dryer 264, the impurity salt containing sodium chloride, sodium sulfate, organic matters and the like is obtained, the impurity salt is burnt in a high temperature incinerator 265 at 300-600 ℃, and the contained organic matters are carbonized, and the salt contents of the sodium chloride, the sodium sulfate and the like are reserved; the carbonized mixed salt is dissolved by adding water through a salt dissolving system 266, sodium chloride and sodium sulfate are dissolved in liquid, carbonized organic matters are insoluble, then filtered through a deslagging system 267, filter residues, namely carbonized organic matters, are discharged and can be used as common solid waste treatment, and the filter residues contain sodium chloride and sodium sulfate and are introduced into a nanofiltration treatment unit 21 for reprocessing, so that the problems caused by direct discharge or return to the system are avoided.

The foregoing description of the preferred embodiments of the utility model is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the utility model.

Claims (11)

1. The high-concentration organic brine treatment system comprises a pretreatment system and a deep treatment system, and is characterized by comprising a concentrated brine regulating tank, a first pretreatment unit, a first-stage reverse osmosis device, a second pretreatment unit, a second-stage reverse osmosis device and a pretreatment liquid regulating tank;

the advanced treatment system comprises a nanofiltration treatment unit, an ozone catalytic oxidation unit, an organic concentration unit, a sodium chloride crystallization unit, a sodium sulfate crystallization unit and a salt mixing treatment unit;

the strong brine outlet of the strong brine regulating tank is communicated with the strong brine inlet of the first pretreatment unit; the treatment liquid outlet of the first pretreatment unit is communicated with the liquid inlet of the first-stage reverse osmosis device; the concentrated water outlet of the first-stage reverse osmosis device is communicated with the liquid inlet of the second pretreatment unit; the treatment liquid outlet of the second pretreatment unit is communicated with the liquid inlet of the secondary reverse osmosis device; the concentrated water outlet of the secondary reverse osmosis device is communicated with the liquid inlet of the pretreatment liquid regulating tank;

the liquid outlet of the pretreatment liquid adjusting tank is communicated with the liquid inlet of the nanofiltration treatment unit; the nanofiltration water outlet of the nanofiltration treatment unit is communicated with the liquid inlet of the ozone catalytic oxidation unit, and the nanofiltration concentrated water outlet of the nanofiltration treatment unit is communicated with the liquid inlet of the organic concentration unit; the treatment liquid outlet of the ozone catalytic oxidation unit is communicated with the liquid inlet of the sodium chloride crystallization unit; the concentrated solution outlet of the organic concentration unit is communicated with the liquid inlet of the sodium sulfate crystallization unit; the mother liquor outlet of the sodium chloride crystallization unit is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit, and the mother liquor outlet of the organic concentration unit is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit; and a filtrate outlet of the salt mixing treatment unit is communicated with a liquid inlet of the nanofiltration treatment unit.

2. The high-concentration organic brine treatment system of claim 1 wherein the first pretreatment unit comprises a two-stage softening desilication high-concentration tank, a first-stage sand filtration tank, a first-stage ultrafiltration device and a resin softening device which are communicated in sequence; the two-stage softening and desilication high-density tank comprises a first-stage softening tank, a first-stage sedimentation tank, a second-stage desilication tank and a second-stage sedimentation tank which are sequentially communicated; the concentrated brine inlet of the primary softening tank is communicated with the concentrated brine outlet of the concentrated brine regulating tank; the liquid outlet of the secondary sedimentation tank is communicated with the liquid inlet of the primary sand filtration tank; the treatment fluid outlet of the resin softening device is communicated with the fluid inlet of the first-stage reverse osmosis device.

3. The high-concentration organic salt water treatment system according to claim 2, wherein the second pretreatment unit comprises a decarburization tower, a decarburization water producing tank, a desilication high-concentration tank, a secondary sand filter tank and a secondary ultrafiltration device which are communicated in sequence; the silicon-removing high-density tank comprises a three-stage silicon-removing tank and a three-stage sedimentation tank which are sequentially communicated; the liquid inlet of the decarburization tower is communicated with the concentrated water outlet of the primary reverse osmosis device; the liquid inlet of the three-stage silicon removal pool is communicated with the liquid outlet of the decarburization water producing pool; the liquid outlet of the third-stage sedimentation tank is communicated with the liquid inlet of the second-stage sand filter tank; the treatment fluid outlet of the secondary ultrafiltration device is communicated with the fluid inlet of the secondary reverse osmosis device.

4. A high concentration organic brine treatment system according to claim 3 wherein said pretreatment system further comprises a sludge treatment system; the sludge outlet of the primary sedimentation tank is communicated with the sludge inlet of the sludge treatment system; the sludge outlet of the secondary sedimentation tank is communicated with the sludge inlet of the sludge treatment system; and a sludge outlet of the three-stage sedimentation tank is communicated with a sludge inlet of the sludge treatment system.

5. The high concentration organic brine treatment system of claim 2 wherein the pretreatment system further comprises a deamination resin tank, a pure water reverse osmosis device and a reverse osmosis water producing tank; the evaporation condensate water outlet of the sodium chloride crystallization unit is communicated with the liquid inlet of the deamination resin tank; the liquid outlet of the deamination resin tank is communicated with the liquid inlet of the pure water reverse osmosis device; the water outlet of the secondary reverse osmosis device is communicated with the liquid inlet of the pure water reverse osmosis device; the concentrated water outlet of the pure water reverse osmosis device is communicated with the liquid inlet of the primary reverse osmosis device; the water outlet of the pure water reverse osmosis device is communicated with the liquid inlet of the reverse osmosis water producing tank; the liquid inlet of the reverse osmosis water producing pool is communicated with the water producing outlet of the first-stage reverse osmosis device.

6. The high-concentration organic brine treatment system of claim 5 wherein the nanofiltration treatment unit comprises a first security filter and at least two stages of nanofiltration membrane devices in sequential communication; the liquid inlet of the first security filter is communicated with the liquid outlet of the pretreatment liquid adjusting tank; the nanofiltration water outlet of the nanofiltration membrane device is communicated with the liquid inlet of the ozone catalytic oxidation unit, and the nanofiltration concentrated water outlet of the nanofiltration membrane device is communicated with the liquid inlet of the organic concentration unit.

7. The high-concentration organic salt water treatment system according to claim 6, wherein the ozone catalytic oxidation unit comprises an ozone generator, a catalytic oxidation reaction device and a tail gas collecting device which are sequentially communicated; the liquid inlet of the catalytic oxidation reaction device is communicated with the nanofiltration water outlet of the nanofiltration membrane device; and a treatment fluid outlet of the catalytic oxidation reaction device is communicated with a fluid inlet of the sodium chloride crystallization unit.

8. The high-concentration organic brine treatment system of claim 7, wherein the sodium chloride crystallization unit comprises a sodium chloride evaporation raw water tank, an MVR falling film concentration device, an MVR evaporation crystallization device, a sodium chloride thickener, a sodium chloride centrifuge, a sodium chloride dry bed and a sodium chloride packing machine which are sequentially communicated; the liquid inlet of the sodium chloride evaporation raw water tank is communicated with the treatment liquid outlet of the catalytic oxidation reaction device; the crystal slurry outlet of the MVR evaporation crystallization device is communicated with the liquid inlet of the sodium chloride thickener; the mother liquor outlet of the MVR evaporation crystallization device is communicated with the mixed salt mother liquor inlet of the mixed salt treatment unit; and an evaporation condensate outlet of the MVR evaporation crystallization device is communicated with a liquid inlet of the deamination resin tank.

9. The system of claim 8, wherein the organic concentration unit comprises a second cartridge filter and an organic membrane concentration device in sequential communication; the liquid inlet of the second security filter is communicated with the nanofiltration concentrated water outlet of the nanofiltration membrane device; the concentrated solution outlet of the organic film concentration device is communicated with the liquid inlet of the sodium sulfate crystallization unit; and a mother liquor outlet of the organic film concentration device is communicated with a mixed salt mother liquor inlet of the mixed salt treatment unit.

10. The high-concentration organic brine treatment system of claim 9, wherein the sodium sulfate crystallization unit comprises a sodium sulfate evaporation raw water tank, a freezing feed tank, a freezing crystallization device, a primary sodium sulfate thickener, a primary sodium sulfate centrifuge, a hot melt crystallization device, a secondary sodium sulfate thickener, a secondary sodium sulfate centrifuge, a sodium sulfate drying bed and a sodium sulfate packaging machine which are sequentially communicated; the liquid inlet of the sodium sulfate evaporation raw water tank is communicated with the concentrated liquid outlet of the organic film concentrating device; the crystal slurry outlet of the freezing crystallization device is communicated with the liquid inlet of the primary sodium sulfate thickener, and the mother liquor outlet of the freezing crystallization device is communicated with the liquid inlet of the first security filter.

11. The high-concentration organic brine treatment system according to claim 10, wherein the salt-mixing treatment unit comprises a salt-mixing evaporation crystallization device, a salt-mixing thickener, a salt-mixing centrifuge, a roller dryer, a high-temperature incinerator, a salt-dissolving system and a slag removal system which are sequentially communicated; the mixed salt mother liquor inlet of the mixed salt evaporation crystallization device is communicated with the mother liquor outlet of the MVR evaporation crystallization device; the mixed salt mother liquor inlet of the roller dryer is communicated with the mother liquor outlet of the organic film concentration device; and a filtrate outlet of the deslagging system is communicated with a liquid inlet of the first security filter.

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