CN113173674A - High-salinity concentrated water recycling treatment system and method - Google Patents
High-salinity concentrated water recycling treatment system and method Download PDFInfo
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- CN113173674A CN113173674A CN202110565308.0A CN202110565308A CN113173674A CN 113173674 A CN113173674 A CN 113173674A CN 202110565308 A CN202110565308 A CN 202110565308A CN 113173674 A CN113173674 A CN 113173674A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000004064 recycling Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 102
- 150000003839 salts Chemical class 0.000 claims abstract description 78
- 239000011780 sodium chloride Substances 0.000 claims abstract description 52
- 238000001728 nano-filtration Methods 0.000 claims abstract description 49
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 44
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 37
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 37
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 36
- 239000012267 brine Substances 0.000 claims abstract description 28
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims description 33
- 230000008020 evaporation Effects 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 32
- 239000003513 alkali Substances 0.000 claims description 28
- 230000008014 freezing Effects 0.000 claims description 24
- 238000007710 freezing Methods 0.000 claims description 24
- 239000012452 mother liquor Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000005684 electric field Effects 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 description 104
- 239000012528 membrane Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 sulfate radical Chemical class 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a high-salinity concentrated water recycling treatment system which comprises a buffer tank, a nanofiltration device and a reverse osmosis device, wherein the buffer tank, the nanofiltration device and the reverse osmosis device are sequentially connected; a concentrated water outlet of the reverse osmosis device is connected with a sodium chloride evaporative crystallizer and a sodium chloride brine tank; the sodium chloride brine tank is also connected with the BPED unit, a brine outlet and an acid-base outlet are arranged on the BPED unit, and the brine outlet of the BPED unit is connected with a pipeline between the reverse osmosis device and the nanofiltration device; a concentrated water outlet of the nanofiltration device is connected with a sodium sulfate treatment unit; the sodium chloride evaporative crystallizer and the sodium sulfate processing unit are both connected with the miscellaneous salt processing unit. Meanwhile, the invention also discloses a treatment method for recycling the high-salinity concentrated water by adopting the treatment system; the treatment system and the treatment method provided by the invention convert the salt into the acid-base product, reduce the purchased amount of the acid-base and realize the resource recycling of the salt.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a treatment system and method for recycling high-salinity concentrated water.
Background
The wastewater generated in the energy chemical production process generally has the characteristics of high salt, high organic matter, high hardness, high silicon content and the like, the industrial wastewater treatment realizes the standard discharge and partial reuse of the wastewater through the wastewater treatment at first, and then the zero discharge of the wastewater is realized according to the further requirements of the environmental protection policy, thereby forming the necessary premise of the construction and operation of energy chemical projects. The separation of water and salt in the waste water can be effectively realized through long series connection combined process units by a general zero discharge system, wherein most suspended matters, scaling ions and organic pollutants in high-concentration brine in chemical production are removed by a front-end main process unit, water and salt are separated by a tail end salt separating technology, and produced water is recycled, so that the resource recycling of the water is basically realized. With the realization of zero discharge of wastewater, the environmental protection department requires to band the salt solarization pool, definitely the miscellaneous salt is solid dangerous waste and to gradually cancel the piling of the miscellaneous salt, and requires the resource utilization of the waste salt slag dissolved in water at the tail end of zero discharge, thereby greatly promoting the innovation and development of technical researchers to develop the waste salt resource utilization process.
Nanofiltration (NF) salt separation, hot salt separation and cold-hot salt separation are common salt separation technologies of zero emission systems in the existing coal chemical industry, wherein a 'NF + evaporation' coupling process is a feasible design of concentrated salt water and salt at the present stage, but in the operation of an actual system, because the front-end treatment is incomplete, the difficulty of nanofiltration salt separation is increased, salt deposition and blockage of an evaporation unit are serious, and the long-period stable operation capacity of the zero emission system is weakened. The generated mixed salt mainly comprises NaCl and Na2SO4The mixed salt is further treated to remove organic impurities and can be used as industrial raw materials, the secondary application and operation cost is relatively high, and the added value of the product is relatively low. The conventional treatment technologies of the waste salt at present comprise pyrolysis, harmless landfill, incineration and the like, and the treatment is inconsistent with the reduction, harmless and resource utilization principles of the waste salt, so that the upstream and downstream industries are disconnected, the comprehensive utilization cannot be realized, and the resource waste is caused.On the other hand, 50-70% of mixed salt obtained by separating the energy chemical wastewater is a product of adding medicament acid and alkali in the industrial production process. Therefore, if the strong brine can be converted into the acid and alkali which can be used by the system, the generated acid and alkali can be used as a main device for adjusting pH, chemically cleaning, regenerating a resin bed and the like, and solid waste and secondary pollution are not generated, the recycling economy of waste salt recycling and energy chemical industry can be fully realized, and the significance is great.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a treatment system and a method for recycling high-salinity concentrated water,
a treatment system for recycling high-salinity concentrated water comprises a buffer tank, a nanofiltration device and a reverse osmosis device which are sequentially connected, wherein a produced water outlet and a concentrated water outlet are formed in the nanofiltration device and the reverse osmosis device respectively, the reverse osmosis device is connected with the produced water outlet of the nanofiltration device, and the produced water outlet of the reverse osmosis device is connected with a reuse water tank;
a concentrated water outlet of the reverse osmosis device is connected with a sodium chloride evaporative crystallizer and a sodium chloride brine tank; the sodium chloride brine tank is also connected with the BPED unit, the BPED unit is provided with a brine outlet and an acid-base outlet, the acid-base outlet of the BPED unit is respectively connected with the acid tank and the base tank through pipelines, and the brine outlet of the BPED unit is connected with a pipeline between the reverse osmosis device and the nanofiltration device;
a concentrated water outlet of the nanofiltration device is connected with a sodium sulfate treatment unit;
the sodium chloride evaporative crystallizer and the sodium sulfate processing unit are both connected with the miscellaneous salt processing unit.
Preferably, the sodium sulfate treatment unit comprises a freezing crystallizer, an ozone catalytic oxidation device and a filter are sequentially connected to the freezing crystallizer, and the filter is also connected with a buffer tank; the freezing crystallizer is also sequentially connected with a hot melting tank and a sodium sulfate evaporation crystallizer; the freezing crystallizer is connected with a concentrated water outlet of the nanofiltration device.
Preferably, the mixed salt treatment unit comprises a mixed salt evaporative crystallizer and a mother liquor drying system which are connected in sequence, and the mixed salt evaporative crystallizer is respectively connected with the sodium chloride evaporative crystallizer and the sodium sulfate evaporative crystallizer.
Preferably, the BPED unit is provided with a pH meter on a pipeline connected with the acid tank and the alkali tank respectively.
Preferably, the filter is a multimedia filter, a V-bank filter or a fiber filter.
Preferably, the miscellaneous salt evaporative crystallizer is a forced circulation evaporative crystallizer.
Preferably, the mother liquor drying system is a vacuum drum dryer or a spray dryer.
A treatment method for recycling high-salinity concentrated water adopts the treatment system for recycling high-salinity concentrated water to treat, and comprises the following steps:
(1) the wastewater enters a nanofiltration device from a buffer tank and is filtered by the nanofiltration device to be subjected to salt separation treatment; the operating pressure of the nanofiltration device is 3.5-30bar, the TDS of the inlet water is 30000-40000mg/L, the recovery rate is 90%, and the sulfate radical rejection rate is more than or equal to 97%;
(2) the produced water filtered by the nanofiltration device enters a reverse osmosis device for concentration, and the reverse osmosis produced water flows into a reuse water tank; part of reverse osmosis concentrated water is decompressed and then enters a BPED unit through a sodium chloride brine tank, generated acid and alkali respectively enter an acid tank and an alkali tank after being detected by a pH meter to meet the acidity requirement under the action of an electric field of the BPED unit, and generated brine flows back to a reverse osmosis device; the other part of the reverse osmosis concentrated water is decompressed and then enters a sodium chloride evaporation crystallizer to generate a sodium chloride product;
(3) the concentrated water filtered by the nanofiltration device enters a sodium sulfide treatment unit, passes through a freezing crystallizer, and the separated crystals enter a hot melting tank and then enter a sodium sulfate evaporation crystallizer to obtain a sodium sulfate product; oxidizing the frozen clear liquid generated by the freezing crystallizer by an ozone catalyst oxidizer to remove COD, filtering by a filter, and refluxing the filtered water to a buffer tank;
(4) mother liquor generated by the sodium chloride evaporation crystallizer and the sodium sulfate evaporation crystallizer enter the mixed salt evaporation crystallizer, and the mother liquor generated by the mixed salt evaporation crystallizer is dried by a mother liquor drying system to obtain the mixed salt.
Preferably, the TDS of the mother liquor generated by the miscellaneous salt evaporative crystallizer is less than or equal to 1000mg/L, COD and less than or equal to 500 mg/L.
Preferably, the mother liquor drying system is a vacuum drum dryer or a spray dryer; the temperature of the vacuum drum dryer is 60-90 ℃, the pressure is 55kPa-70kPa, and the clearance between the scraper and the drum is not less than 0.6 mm.
The BPED of the invention is bipolar membrane electrodialysis.
The invention has the advantages that:
1. the treatment system and the method provided by the invention convert the salt into acid-base products, and the generated acid-base can be used for sewage acid-base regulation, ion exchange resin regeneration, chemical cleaning and the like in a park, so that the purchased amount of the acid-base is reduced, and the resource recycling of the salt is realized;
2. the salt is separated by nanofiltration and is electrolyzed by the BPED membrane stack, so that the resource utilization rate of the salt is improved, the generation of the amount of miscellaneous salt is reduced, and the disposal cost of solid waste is reduced.
Drawings
FIG. 1 is a schematic view of a treatment system for recycling high-salinity concentrated water according to the present invention;
the device comprises a buffer tank 1, a nanofiltration device 2, a reverse osmosis device 3, a sodium chloride brine tank 4, a BPED 5, an acid tank 6, an alkali tank 7, a sodium chloride evaporative crystallizer 8, a miscellaneous salt evaporative crystallizer 9, a mother liquor drying system 10, a freezing crystallizer 11, an ozone catalytic oxidizer 12, a filter 13, a hot melting tank 14, a sodium sulfate evaporative crystallizer 15 and a recycling water tank 16.
Detailed Description
Example 1
A treatment system for recycling high-salinity concentrated water comprises a buffer tank 1, a nanofiltration device 2 and a reverse osmosis device 3 which are sequentially connected, wherein both the nanofiltration device 2 and the reverse osmosis device 3 are provided with a produced water outlet and a concentrated water outlet, the reverse osmosis device 3 is connected with the produced water outlet of the nanofiltration device 2, and the produced water outlet of the reverse osmosis device 3 is connected with a reuse water tank 16;
a concentrated water outlet of the reverse osmosis device 3 is connected with a sodium chloride evaporative crystallizer 8 and a sodium chloride brine tank 4; the sodium chloride brine tank 4 is also connected with a BPED unit 5, a brine outlet and an acid-base outlet are formed in the BPED unit 5, the acid-base outlet of the BPED unit 5 is respectively connected with an acid tank 6 and an alkali tank 7 through pipelines, the brine outlet of the BPED unit 5 is connected with a pipeline between the reverse osmosis device 3 and the nanofiltration device 2, and brine generated by the BPED unit 5 flows back to the reverse osmosis device 3;
a concentrated water outlet of the nanofiltration device 2 is connected with a sodium sulfate treatment unit, and the sodium sulfate treatment unit is used for treating concentrated water generated by nanofiltration to obtain sodium sulfate;
the sodium chloride evaporative crystallizer 8 and the sodium sulfate processing unit are both connected with the mixed salt processing unit, and the mixed salt processing unit further processes the liquid discharged by the sodium chloride evaporative crystallizer 8 and the sodium sulfate processing unit to recover the salt in the liquid.
In the embodiment, the high-salinity wastewater is separated from monovalent salt and divalent salt through a nanofiltration device 2, divalent ions are mainly used in nanofiltration concentrated water, salt components mainly comprise sodium sulfate and a small amount of sodium chloride; the main salt component in the nanofiltration product water is monovalent salt sodium chloride, after further concentration by reverse osmosis, the reverse osmosis product water enters a reuse water tank 16, and the reverse osmosis concentrated water enters a BPED unit, so that the sodium chloride solution entering the BPED is ensured to be in a reasonable concentration range; after the reverse osmosis concentrated water is decompressed, one part of the reverse osmosis concentrated water enters the BPED through the sodium chloride brine tank 4, and the sodium chloride brine tank 4 can ensure the stable water coming from the BPED; the other part enters a sodium chloride evaporative crystallizer 8, and sodium chloride products are separated after evaporative crystallization;
under the action of a direct current electric field, chloride ions migrate to an acid chamber through a negative membrane in BPED, and when encountering a positive membrane surface of the bipolar membrane, the chloride ions cannot continuously migrate due to the negative charge of the positive membrane surface, remain in the acid chamber and combine with hydrogen ions decomposed from the positive membrane surface of the bipolar membrane to generate hydrochloric acid; similarly, sodium ions migrate to the alkaline chamber through the positive membrane and meet the negative membrane surface of the bipolar membrane, and because the positive electricity is generated on the positive membrane surface, the sodium ions cannot continuously migrate and are left in the alkaline chamber to be combined with hydroxide ions continuously decomposed from the negative membrane surface of the bipolar membrane under the action of the direct-current electric field to generate sodium hydroxide; thus, acid radical ions in the salt chamber continuously enter the acid chamber, so that the concentration of the acid liquor is continuously improved; sodium ions continuously enter the alkali chamber to receive hydroxide ions decomposed by the bipolar membrane, and the concentration of the alkali solution is continuously improved. Finally, sodium chloride is converted into hydrochloric acid and sodium hydroxide solution through bipolar membrane electrodialysis.
Example 2
On the basis of embodiment 1, the sodium sulfate treatment unit comprises a freezing crystallizer 11, an ozone catalytic oxidation device 12 and a filter 13 are sequentially connected to the freezing crystallizer 11, and the filter 13 is also connected to the buffer tank 1; the freezing crystallizer 11 is also sequentially connected with a hot melting tank 14 and a sodium sulfate evaporation crystallizer 15; the freezing crystallizer 11 is connected with a concentrated water outlet of the nanofiltration device 2.
In the embodiment, nanofiltration concentrated water passes through a freezing crystallizer 11, the solubility of sodium sulfate is rapidly reduced along with the reduction of the temperature at 0-100 ℃ by utilizing the principle of the solubility difference of sodium sulfate and sodium chloride in a low-temperature medium, and the sodium chloride is basically kept unchanged, so that sodium sulfate decahydrate crystals are crystallized and separated out in a cooling and freezing mode; the frozen clear liquid generated by freezing crystallization is subjected to ozone oxidation to remove COD in the frozen clear liquid, is further filtered by a filter 13 and returns to the buffer tank 1; sodium sulfate decahydrate crystals separated by freezing crystallization are subjected to hot melting in a hot melting tank 14, and then are subjected to evaporation crystallization to obtain sodium sulfate salt.
Example 3
On the basis of embodiment 2, the mixed salt treatment unit comprises a mixed salt evaporative crystallizer 9 and a mother liquor drying system 10 which are sequentially connected, wherein the mixed salt evaporative crystallizer 9 is respectively connected with a sodium chloride evaporative crystallizer 8 and a sodium sulfate evaporative crystallizer 15.
Mother liquor discharged from the sodium chloride evaporation crystallizer 8 and the sodium sulfate evaporation crystallizer 15 enters the mixed salt evaporation crystallizer 9 to separate out mixed salt, and the mother liquor discharged from the mixed salt evaporation crystallizer 9 is dried to further recover the mixed salt.
Example 4
On the basis of embodiment 3, the pipelines of the BPED unit 5 connected with the acid tank 6 and the alkali tank 7 are respectively provided with a pH meter, and when the generated acid and alkali reach the required concentration, the generated acid and alkali are respectively conveyed to the acid tank 6 and the alkali tank 7.
Example 5
On the basis of the embodiment 4, the filter 13 is a multi-media filter, a V-shaped filter pool or a fiber filter; the miscellaneous salt evaporative crystallizer 9 is a forced circulation evaporative crystallizer; the mother liquor drying system 10 is a vacuum drum dryer or a spray dryer.
Example 6
A treatment method for recycling high-salinity concentrated water adopts the treatment system for recycling high-salinity concentrated water to treat, and comprises the following steps:
(1) the wastewater enters a nanofiltration device 2 from a buffer tank 1 and is filtered by the nanofiltration device 2 to be subjected to salt separation treatment; the operating pressure of the nanofiltration device 2 is 3.5-30bar, the TDS of the inlet water is 30000-40000mg/L, the recovery rate is 90%, and the sulfate radical rejection rate is more than or equal to 97%;
(2) the produced water filtered by the nanofiltration device 2 enters a reverse osmosis device 3 for concentration, and the reverse osmosis produced water flows into a reuse water tank 16; part of reverse osmosis concentrated water is decompressed and then enters a BPED unit 5 through a sodium chloride brine tank 4, under the action of an electric field of the BPED unit 5, generated acid and alkali reach acidity requirements through pH meter detection and then respectively enter an acid tank 6 and an alkali tank 7, and generated brine flows back to a reverse osmosis device 3; the other part of the reverse osmosis concentrated water enters a sodium chloride evaporation crystallizer 8 after being decompressed to generate a sodium chloride product, wherein the quality of the sodium chloride product is not lower than the index requirement of a first-grade industrial wet salt in the GBT5462-2015 standard of Industrial salt;
(3) the concentrated water filtered by the nanofiltration device 2 enters a sodium sulfide treatment unit, passes through a freezing crystallizer 11, and the separated crystals enter a hot melting tank 14 and then enter a sodium sulfate evaporation crystallizer 15 to obtain a sodium sulfate product; the frozen clear liquid generated by the freezing crystallizer 11 is oxidized by an ozone catalyst oxidizer to remove COD, and then is filtered by a filter 13, the filtered water flows back to a buffer tank 1, and the quality of the product sodium sulfate is not lower than the standard requirement of second-class qualified products in the standard of GBT 6009-;
(4) mother liquor generated by the sodium chloride evaporation crystallizer 8 and the sodium sulfate evaporation crystallizer 15 enters the mixed salt evaporation crystallizer 9, and the mother liquor generated by the mixed salt evaporation crystallizer 9 is dried by the mother liquor drying system 10 to obtain the mixed salt.
Example 7
Taking a zero emission project of a sewage plant in a certain petrochemical industry base as an example, the method of the embodiment 6 is adopted, the adopted mother liquor drying system 10 is a vacuum drum dryer, the temperature of the vacuum drum dryer is 60-90 ℃, the pressure is 55kPa-70kPa, and the clearance between a scraper and a drum is not less than 0.6 mm; nanofiltration influent TDS 35500mg/L and water amount 241m3The recovery rate is 90%, the TDS of the BPED inlet water is 10.9 ten thousand mg/L, and the quality of other inlet water is shown in Table 1.
The mixture enters a BPED unit to separate 8 percent of sodium hydroxide product and 7.3 percent of hydrochloric acid product, and 22.5 tons of 7.3 percent hydrochloric acid is produced per hour, and 22.5 tons of 8.0 percent sodium hydroxide is produced per hour;
TDS of mother liquor generated by the miscellaneous salt evaporation crystallizer is less than or equal to 1000mg/L, COD and less than or equal to 500 mg/L;
the water inflow of the sodium chloride evaporative crystallizer is 23.7m3The TDS of the inlet water is 10.9 ten thousand mg/L, and 2.2 tons of sodium chloride are produced per hour; the water inflow of the freezing crystallizer is 24.1m3The TDS is 7.6 ten thousand mg/L, and 1.46 tons of sodium sulfate is produced per hour; 0.64 ton of miscellaneous salt;
the final acid and alkali yield and the garden requirement after treatment are shown in the following table 2, and the acid yield is higher than the acid yield required by the garden and the alkali yield is lower than the alkali yield required by the garden by the treatment method of the invention, so that the medicament cost and the solid waste treatment cost are fully reduced.
The implementation effect is as follows: the BPED process is adopted to prepare acid and alkali from sodium chloride, the acid and alkali can be reused in sewage plants in chemical industrial parks or industrial parks, in the aspect of operation, the amount of the acid and alkali saved is 3-4 yuan/t water, partial energy consumption of the BPED can be offset, the amount of miscellaneous salt is greatly reduced, and produced acid and alkali products can be completely applied to the sewage plants in the parks, so that the acid and alkali consumption in the parks is reduced, and the problem of unsmooth sale of a large amount of product salt (sodium chloride) can be avoided.
Claims (10)
1. The utility model provides a processing system of concentrated water resourceization of high salt which characterized in that: the device comprises a buffer tank (1), a nanofiltration device (2) and a reverse osmosis device (3) which are connected in sequence, wherein a produced water outlet and a concentrated water outlet are respectively arranged on the nanofiltration device (2) and the reverse osmosis device (3), the reverse osmosis device (3) is connected with the produced water outlet of the nanofiltration device (2), and the produced water outlet of the reverse osmosis device (3) is connected with a reuse water tank (16); a concentrated water outlet of the reverse osmosis device (3) is connected with a sodium chloride evaporative crystallizer (8) and a sodium chloride brine tank (4); the sodium chloride brine tank (4) is also connected with a BPED unit (5), a brine outlet and an acid-base outlet are formed in the BPED unit (5), the acid-base outlet of the BPED unit (5) is respectively connected with an acid tank (6) and an alkali tank (7) through pipelines, and the brine outlet of the BPED unit (5) is connected with a pipeline between the reverse osmosis device (3) and the nanofiltration device (2); a concentrated water outlet of the nanofiltration device (2) is connected with a sodium sulfate treatment unit; the sodium chloride evaporative crystallizer (8) and the sodium sulfate processing unit are both connected with the mixed salt processing unit.
2. The high-salinity concentrated water recycling treatment system according to claim 1, characterized in that: the sodium sulfate treatment unit comprises a freezing crystallizer (11), an ozone catalytic oxidation device (12) and a filter (13) are sequentially connected to the freezing crystallizer (11), and the filter (13) is also connected with the buffer tank (1); the freezing crystallizer (11) is also sequentially connected with a hot melting tank (14) and a sodium sulfate evaporation crystallizer (15); the freezing crystallizer (11) is connected with a concentrated water outlet of the nanofiltration device (2).
3. The high-salinity concentrated water recycling treatment system according to claim 2, characterized in that: the mixed salt treatment unit comprises a mixed salt evaporation crystallizer (9) and a mother liquor drying system (10) which are sequentially connected, wherein the mixed salt evaporation crystallizer (9) is respectively connected with a sodium chloride evaporation crystallizer (8) and a sodium sulfate evaporation crystallizer (15).
4. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: and the BPED unit (5) is respectively provided with a pH meter on a pipeline connected with the acid tank (6) and the alkali tank (7).
5. The high-salinity concentrated water recycling treatment system according to claim 2, characterized in that: the filter (13) is a multi-media filter, a V-shaped filter or a fiber filter.
6. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: the miscellaneous salt evaporative crystallizer (9) is a forced circulation evaporative crystallizer.
7. The high-salinity concentrated water recycling treatment system according to claim 3, characterized in that: the mother liquor drying system (10) is a vacuum drum dryer or a spray dryer.
8. A treatment method for recycling high-salinity concentrated water is characterized by comprising the following steps: the high-salinity concentrated water recycling treatment system of claim 4 is adopted for treatment, and comprises the following steps: (1) the wastewater enters a nanofiltration device (2) from a buffer tank (1) and is filtered by the nanofiltration device (2) for salt separation treatment; the operating pressure of the nanofiltration device (2) is 3.5-30bar, the TDS of the inlet water is 30000-40000mg/L, the recovery rate is 90%, and the retention rate of sulfate radicals is more than or equal to 97%;
(2) the produced water filtered by the nanofiltration device (2) enters a reverse osmosis device (3) for concentration, and the reverse osmosis produced water flows into a reuse water tank (16); part of reverse osmosis concentrated water is decompressed and then enters a BPED unit (5) through a sodium chloride brine tank (4), generated acid and alkali respectively enter an acid tank (6) and an alkali tank (7) after being detected by a pH meter under the action of an electric field of the BPED unit (5), and generated brine flows back to a reverse osmosis device (3); the other part of the reverse osmosis concentrated water enters a sodium chloride evaporation crystallizer (8) after being decompressed to generate a sodium chloride product;
(3) concentrated water filtered by the nanofiltration device (2) enters a sodium sulfide treatment unit, passes through a freezing crystallizer (11), and separated crystals enter a hot melting tank (14) and then enter a sodium sulfate evaporation crystallizer (15) to obtain a sodium sulfate product; the frozen clear liquid generated by the freezing crystallizer (11) is oxidized by an ozone catalyst oxidizer to remove COD, and then is filtered by a filter (13), and the filtered water flows back to the buffer tank (1);
(4) mother liquor generated by the sodium chloride evaporation crystallizer (8) and the sodium sulfate evaporation crystallizer (15) enters the mixed salt evaporation crystallizer (9), and the mother liquor generated by the mixed salt evaporation crystallizer (9) is dried by a mother liquor drying system (10) to obtain the mixed salt.
9. The method for recycling the high-salinity concentrated water according to claim 8, characterized in that: the TDS of the mother liquor generated by the miscellaneous salt evaporative crystallizer (9) is less than or equal to 1000mg/L, COD and less than or equal to 500 mg/L.
10. The method for recycling the high-salinity concentrated water according to claim 9, characterized in that: the mother liquor drying system (10) is a vacuum rotary drum dryer or a spray dryer; the temperature of the vacuum drum dryer is 60-90 ℃, the pressure is 55kPa-70kPa, and the clearance between the scraper and the drum is not less than 0.6 mm.
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