WO2012155607A1 - 一种基于电解和双膜技术的再生水制造装置及其方法 - Google Patents

一种基于电解和双膜技术的再生水制造装置及其方法 Download PDF

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WO2012155607A1
WO2012155607A1 PCT/CN2012/072014 CN2012072014W WO2012155607A1 WO 2012155607 A1 WO2012155607 A1 WO 2012155607A1 CN 2012072014 W CN2012072014 W CN 2012072014W WO 2012155607 A1 WO2012155607 A1 WO 2012155607A1
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water
electrolysis
reverse osmosis
membrane
mbr
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PCT/CN2012/072014
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English (en)
French (fr)
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张世文
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波鹰(厦门)科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a high-purity reclaimed water manufacturing device and a method thereof, in particular to a high-purity reclaimed water manufacturing device and a method thereof combined with an electrolysis technology and a double membrane technology.
  • Chinese patent CN200410024576.8 discloses 'a process and special equipment for sewage extraction and reclaimed water', which is after the sewage has been treated by enzymes. A method of producing reclaimed water by filtration and ozone sterilization.
  • Chinese patent CN101108760B discloses a method for recycling reclaimed water through continuous microfiltration treatment of sewage that has reached the discharge standard after biochemical treatment. It uses the tail water of biochemical effluent as the source water, passes through the swirling coagulation reaction tank, and the advection multi-dump sedimentation tank.
  • the quality of the reclaimed water is not high: firstly, it is difficult to remove the residual color and odor in the sewage by the existing sewage purification and regeneration technology, and the residual water remains. There are various nutrients and bacteria, molds, algae, etc., when exposed to appropriate temperature and light conditions, they will rapidly multiply and cause black body odor, and produce difficult-to-handle biological scale, which will also have adverse effects on process equipment.
  • the application of reclaimed water in industrial production is very limited; secondly, the total dissolved salt content in the sewage is high, and contains a large amount of calcium and magnesium salts which can form scale. When it is transported to the water processing equipment through the pipeline, it will be long-term.
  • Electrochemical corrosion damage caused by the use of water equipment, as the calcium and magnesium salts in the water are continuously circulated and concentrated in the water equipment, further forming scale, which may cause blockage of water equipment.
  • economically uneconomical after biochemical treatment through multi-stage membrane, although the sewage can be regenerated, but the one-time equipment investment is large, the operating cost is higher than the current tap water price, from the economical standard, still not satisfactory, reclaimed water Processing recycling can not achieve scale.
  • Secondary pollution The traditional reclaimed water reuse technology usually uses the flocculant and bactericide to precipitate the microorganisms, colloids and solid particles in the water, and then passes through the sand filter, multi-media filtration and membrane filtration.
  • the purification process has the disadvantages of adding flocculant and disinfectant during the treatment process, which not only has large investment and high running cost, but also causes flocculation and bactericide to cause different degrees of pollution to the environment. From the above problems, we can study and develop safe, reliable, high-efficiency, low-energy, low-investment, low-cost reclaimed water recycling technologies and supporting equipment suitable for China's economic status and development level, laying the foundation for the scale and industrialization of recycled water reuse. A solid foundation has become an urgent task.
  • the object of the present invention is to solve the problems existing in the existing sewage recycling and recycling technology, and to provide a water quality requirement for the production process water which can overcome the poor quality of the reclaimed water in the existing sewage regeneration technology and is difficult to meet the industrial production, and has large investment and operating cost. High and secondary pollution to the environment, which can reduce sewage discharge and improve water use efficiency. Reclaimed water manufacturing equipment based on electrolysis and double membrane technology.
  • Another object of the present invention is to provide a method for producing reclaimed water based on electrolysis and double membrane technology.
  • the invention relates to a high-purity reclaimed water manufacturing device and method for deep purification treatment of sewage (referred to as biochemical effluent or deep treatment discharge sewage) which is subjected to biochemical treatment after industrial sewage and urban domestic sewage are subjected to biochemical treatment.
  • biochemical effluent or deep treatment discharge sewage referred to as biochemical effluent or deep treatment discharge sewage
  • the reclaimed water manufacturing device based on the electrolysis and double membrane technology of the present invention is provided with an electrolysis system, a membrane bioreactor system (hereinafter referred to as MBR system) and a reverse osmosis system;
  • MBR system membrane bioreactor system
  • reverse osmosis system a membrane bioreactor system
  • the electrolysis system is used for electrolytic treatment of the deep treated sewage, the electrolysis system is provided with a shut-off valve, a water supply pump and an electrolysis machine; the inlet of the shut-off valve is externally connected with a biochemical water discharge port, the inlet of the water supply pump is connected to the outlet of the shut-off valve, and the water supply pump The outlet of the electrolyzer is connected to the inlet of the electrolysis machine, and the outlet of the electrolysis machine is connected with the inlet of the MBR system;
  • the electrolysis machine is provided with a power source and an electrolysis tank.
  • the anode material in the electrolysis tank is one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, metal alloy and nano catalytic inert anode.
  • the surface layer of the nano catalytic inert anode is coated with a metal oxide inert catalytic coating having a crystal grain size of 10 to 35 nm, and the substrate of the nano catalytic inert anode may be a titanium plate or a plastic plate, etc.
  • the high electrocatalytic activity can greatly reduce the overpotential of electrolysis and reduce the occurrence of side reactions.
  • the MBR system is used for further processing the purified sewage obtained by the electrolysis system, and the MBR system is provided with a shut-off valve, a grid, an MBR reaction tank, an MBR membrane module, a blower, an aerator, a sewage pump, a water pump, and a primary reclaimed water storage tank.
  • the inlet of the shut-off valve is connected to the outlet of the electrolysis machine of the electrolysis system, the outlet of the shut-off valve is connected to the inlet of the grid, the outlet of the grid is connected to the inlet of the MBR reaction tank, and the MBR membrane module is submerged in the MBR reaction tank,
  • the blower and the distributed aerator are aerated, the filtrate (water) outlet of the MBR reaction tank is connected to the inlet of the water pump, the outlet of the outlet pump is connected to the inlet of the primary reclaimed water storage tank, and the filtrate collected by the primary reclaimed water storage tank (water ) used for further desalting of the reverse osmosis system for high-purity reclaimed water for recycling in production.
  • the sludge outlet of the MBR reaction tank is connected to the inlet of the sewage pump, and a small amount of sludge is pumped and discharged through the sewage pump; the MBR membrane module is optional.
  • the membrane pore size of the MBR membrane module is 0.10 to 0.2 ⁇ m, and the solid-liquid separation can be performed efficiently, the working pressure is -1 to -50 kPa, and the working temperature is 5 to 45 ° C, suitable for pH 1 ⁇ 14, the fixed suspension of effluent can be reduced to 1mg / L, turbidity can be reduced to below 1NTU.
  • the system can completely remove bacteria and E. coli in sewage, the effluent coliform group is 0, and the total number of colonies is less than 1 CFU/mL;
  • the MBR cleaning system is used to clean the MBR membrane module, and the MBR cleaning system is provided with a cleaning liquid tank.
  • the reverse osmosis system is used for filtering and separating the primary reclaimed water obtained by the MBR system treatment to obtain dialysis water (reclaimed water) and concentrated water.
  • the reverse osmosis membrane system is provided with a shut-off valve, a water supply pump, a security filter, a high pressure pump, a reverse osmosis membrane module, and a reclaimed water storage tank.
  • the inlet of the shut-off valve is connected to the purified sewage outlet of the primary reclaimed water storage tank of the MBR system.
  • the outlet of the shut-off valve enters the reverse osmosis membrane module through the water supply pump, the security filter and the high pressure pump, and the dialysis water outlet of the reverse osmosis membrane module is connected to the reclaimed water storage tank. Imports.
  • the reverse osmosis system passes the primary reclaimed water obtained by the MBR system through the security filter and then pumps it into the reverse osmosis system by high pressure pump.
  • the dialysis water (reclaimed water) and concentrated water are separated by filtration through reverse osmosis membrane, and the dialysis water enters the storage tank to obtain high purity reclaimed water; Part of the water is refluxed by a concentrated water booster pump for filtration by a circulating membrane, and a part of the reflux is recycled into the electrolysis process, and the excess is discharged;
  • the reverse osmosis system further comprises a reverse osmosis concentrate recovery system, a reverse osmosis concentrate membrane recovery system is used for recycling the concentrated water filtered by the reverse osmosis membrane, and the reverse osmosis concentrate recovery system is provided with a reflux concentrated water pressurization system.
  • the electrolysis system is reused.
  • the reverse osmosis system further comprises a reverse osmosis membrane cleaning regeneration system, the reverse osmosis membrane cleaning regeneration system is used for cleaning the reverse osmosis filtration membrane system, and the reverse osmosis membrane cleaning regeneration system is provided with a cleaning liquid tank, a backwashing pump and a shut-off valve, and cleaning
  • the inlet of the liquid tank is connected to the dialysis water outlet of the reverse osmosis membrane system via a shut-off valve, and the outlet of the cleaning liquid tank is connected to the concentrated water outlet of the reverse osmosis system, and the other outlet of the cleaning liquid tank is connected to the water supply pump outlet through the backwash pump.
  • the method for producing reclaimed water based on electrolysis and double membrane technology of the present invention comprises the following steps:
  • Electrolysis After the biochemical effluent is extracted by water pump, it is input into the electrolysis machine for electrolysis, and then enters the MBR system through the grid to remove the dead bodies of bacteria, bacteria and large particles of solid impurities generated by electrolysis.
  • the colloidal substance has to purify the sewage;
  • the biochemical effluent refers to sewage that has been biochemically treated to meet the third-level discharge standard of GB 18918-2002 “Emission Standard for Pollutants in Urban Sewage Treatment Plants”, and its COD Cr ⁇ 120mg/L, BOD5 ⁇ 60 mg /L, SS ⁇ 50mg/L, color ⁇ 50, animal and vegetable oil ⁇ 20mg/L, petroleum ⁇ 15mg/L, anionic surfactant ⁇ 5 mg/L, ammonia nitrogen ⁇ 25mg/L, total phosphorus ⁇ 5 mg/ L, the electrical conductivity is less than 1500 ⁇ s / cm; the electrolysis is to electrolyze the biochemical water to produce nascent chlorine [Cl], hydroxyl [OH] and nascent oxygen [O], for oxidative decomposition of sewage Organic substances such as vegetable oil, petroleum, anionic surfactant, colored substance and ammonia nitrogen, and kill microorganisms in the sewage, and at the same time,
  • MBR system filtration the purified sewage treated by the electrolysis system is flowed into the MBR system through the pipeline, and the primary reclaimed water is separated by the MBR system treatment;
  • the MBR system is a novel wastewater treatment technology organically combined with membrane separation technology and biotechnology, which utilizes a membrane separation device to intercept activated sludge and macromolecular organic substances in a biochemical reaction tank, and has adaptability. Strong, biochemical efficiency, strong impact resistance, small footprint, and good treatment effect.
  • Reverse osmosis desalination The primary reclaimed water filtered by the MBR system is pumped into the reverse osmosis system through a high pressure pump, desalted by reverse osmosis membrane filtration, and the dialysis water and concentrated water are separated, and the dialysis water enters the storage tank to obtain high purity reclaimed water.
  • the working condition of the reverse osmosis system is: normal temperature ⁇ 45 ° C, working pressure is 5 ⁇ 35 kPa; reverse osmosis membrane of the reverse osmosis system is a reverse osmosis membrane with a rejection rate of 98% sodium chloride,
  • the structure of the membrane module is a roll membrane module or a tubular membrane module, and the membrane material is a cellulose acetate membrane or a composite membrane, and the membrane material may have a molecular weight cutoff of 50 to 200 MWCO.
  • the technical scheme of the invention is: sewage after biochemical treatment ⁇ electrolysis ⁇ MBR system ⁇ reverse osmosis system ⁇ high purity reclaimed water.
  • the high-purity reclaimed water has good water quality, and the indicators are far superior to GB/T19923-2005 "Urban Sewage Recycling
  • the standard of industrial water quality can be used as the industrial production process water in various industries, that is, it can be directly applied to the industrial production process to achieve the purpose of clean production.
  • the technical route is used to solve the existing technical problems of wastewater reuse, and has the following advantages:
  • the invention adopts the method of electrolysis, and has the following outstanding effects: (1) electrolysis causes the macromolecule remaining in the sewage to be opened or broken under the action of current to enhance the biodegradability of the sewage; (2) electrolysis generated The nascent chlorine [Cl], hydroxyl [OH] and nascent oxygen [O] oxidize and decompose organic matter to rapidly reduce COD Cr ; (3) oxidize and decompose ammonia nitrogen in sewage, further oxidize residual ammonia nitrogen, and remove ammonia nitrogen The rate can reach 80-90%, while eliminating the odor in the water. (4) Substantially reduce the color of the sewage.
  • the chromaticity of the secondary settling tank is between 80 and 300.
  • the general treatment method is difficult to further remove the chroma, after electrolysis.
  • the chromaticity of the sewage can be reduced from 80 to 300 to 16 to 32.
  • the purified sewage is removed by filtration through a subsequent MBR system.
  • the heavy metal ions in the sewage move to the cathode of the electrolysis cell of the electrolysis machine to form a precipitate at the cathode, thereby reducing the heavy metal ion content in the sewage.
  • high water reuse rate, low cost the reuse rate of sewage is as high as 70% to 90%, less sewage, low energy consumption, high-purity reclaimed water production cost is less than 1 yuan / ton, far lower than the current tap water price.
  • High water quality for reuse The high-purity reclaimed water produced by this technical route is colorless and odorless.
  • the main indicators of water quality are shown in Table 1, which can meet the water quality requirements of industrial water in various industries.
  • Table 1 High purity recycled water quality indicators project concentration project concentration pH value 6.5 ⁇ 8.5 Conductivity ⁇ 300 ⁇ S/cm Turbidity ⁇ 1 chloride ⁇ 50 mg/L Chroma ⁇ 3 times (dilution factor) Total iron ⁇ 0.05mg/L COD Cr ⁇ 10mg/L manganese ⁇ 0.1mg/L SS (suspended matter) ⁇ 2mg/L Free chlorine ⁇ 0.1mg/L Total alkalinity ⁇ 50mg/L (based on calcium carbonate hardness) total hardness ⁇ 10mg/L (based on calcium carbonate hardness)
  • the MBR system uses membrane separation equipment to intercept activated sludge and macromolecular organic matter in the biochemical reaction tank. It has high biochemical efficiency, strong resistance to load shock, low operating pressure, and reverse osmosis system unit. The water production is high, the impurities are removed thoroughly, the energy consumption is small, and the energy consumption of the equipment is greatly reduced during operation.
  • FIG. 1 is a schematic view showing the structural composition of an embodiment of a reclaimed water producing apparatus based on electrolysis and double membrane technology according to the present invention.
  • the invention is designed to purify and regenerate the biochemical effluent after the in-depth systematic comparative study on the composition, properties and existing treatment schemes of the biochemical effluent of the existing sewage treatment plant, through electrolysis, MBR A combination of systems, reverse osmosis systems, and the like, to form a high purity reclaimed water manufacturing apparatus and method.
  • FIG. 1 an embodiment of a high-purity reclaimed water manufacturing apparatus and method based on electrolysis and double membrane technology according to the present invention is provided with:
  • Electrolysis system The electrolysis system is used for electrolytic treatment, and the electrolysis system is provided with a shut-off valve 11, a water supply pump 12, and an electrolysis machine 13 .
  • Shut-off valve The inlet of 11 is externally connected to the biochemical water discharge port, the inlet of the water supply pump 12 is connected to the outlet of the shut-off valve 11, the outlet of the water supply pump 12 is connected to the inlet of the electrolysis machine 13, and the outlet of the electrolysis machine 13 is connected with the MBR.
  • the water inlet of the system is connected.
  • MBR system The MBR system is used to further treat the purified sewage from the electrolysis system.
  • the inlet of the shutoff valve 21 is connected to the outlet of the electrolysis machine 13
  • the outlet of the shutoff valve 21 is connected to the inlet of the grille 22, and the outlet of the grille 22 is sequentially passed through the MBR reaction tank 26 and the water pump 28 Enter the primary reclaimed water storage tank 29 .
  • MBR cleaning system MBR cleaning system is used to clean MBR system, with cleaning liquid tank 31, backwashing pump 32 And shut-off valve 33.
  • the outlet of the cleaning liquid tank 31 is connected to the inlet of the backwashing pump 32
  • the outlet of the backwashing pump 32 is connected to the inlet of the shut-off valve 33
  • the outlet of the shut-off valve 33 is connected to the MBR reaction tank 23 Export.
  • Reverse osmosis system reverse osmosis system for MBR
  • the primary regenerated water obtained by the system treatment is filtered, and dialysis water and concentrated water are separated.
  • the reverse osmosis system is provided with a shut-off valve 41, a water supply pump 42, a shut-off valve 43, a security filter 44, and a membrane system high pressure pump. , reverse osmosis membrane system 46, shut-off valve 47 and reclaimed water storage tank 48.
  • the inlet of the shut-off valve 41 is connected to the outlet of the primary reclaimed water storage tank 28 of the MBR system, and the shut-off valve 41
  • the outlet is sequentially passed through a water supply pump 42, a shut-off valve 43, a safety filter 44, and a membrane system high pressure pump 45 to the reverse osmosis membrane system 46, and the dialysis water outlet of the reverse osmosis membrane system 46 is passed through a shut-off valve. 47
  • Reverse osmosis concentrate recovery system is a system for recycling concentrated water by reverse osmosis membrane filtration.
  • Reverse osmosis membrane recovery system with reflux concentrated water booster pump 51, valve 52, shut-off valve 53 and valve 54.
  • the inlet of the reflux concentrated water booster pump 51 is connected to the concentrated water outlet of the reverse osmosis membrane system 46, and the outlet of the reflux concentrated water booster pump 51 is connected to the reverse osmosis membrane system 46
  • the inlet of the reverse osmosis membrane system 46 is passed through the valve 52, the shut-off valve 53 , the valve 54 and the reflux electrolysis machine 13 for reuse.
  • Reverse osmosis membrane cleaning and regeneration system is used for cleaning reverse osmosis membrane system, reverse osmosis membrane cleaning and regeneration system is provided with shut-off valve 61 and cleaning fluid tank 62.
  • the inlet of the cleaning liquid tank 62 is connected to the dialysis water outlet of the reverse osmosis membrane system 46 via the shutoff valve 61.
  • the outlet of the cleaning liquid tank 62 is connected to the concentrated water outlet of the reverse osmosis membrane system 46 via the shutoff valve 63 and the valve 52.
  • the cleaning liquid tank 62 The other outlet is passed through the shutoff valve 64, all the way through the backwash pump 65 and the shutoff valve 66 is connected to the outlet of the water supply pump 42.
  • the water quality of the sewage is shown in Table 2.
  • Step 1 Electrolysis: The water supply pump 12 is started, and the sewage enters the electrolysis machine 13 through the shut-off valve 11 at a flow rate of 25 m 3 /h for electrolysis.
  • the working voltage of the electrolysis is 12V
  • the voltage between the two electrodes is 3.5 to 8.0V
  • the current density is 130 mA/cm 2 .
  • the nascent chlorine [Cl], hydroxyl [OH] and nascent Strong oxidizing substances such as oxygen [O] can kill plankton and bacteria in sewage, and can open or break macromolecules in sewage, and decompose macroscopic substances that are difficult to biodegrade into small molecular substances.
  • Step 2 MBR system filtration separation: the purified sewage after electrolysis passes through the grid 21 The solid impurities and colloids of the larger particles generated by electrolysis in the sewage are removed by filtration, and then enter the MBR reaction tank 26, and the blower 24 and the aerator 25 are activated. After the aeration is oxidized, the water pump is started. Under negative pressure, water molecules are separated by the MBR membrane module 23 to obtain dialysis water, and the dialyzed water is collected into the primary reclaimed water storage tank 29.
  • the membrane material of the MBR system is a polyvinylidene fluoride (PVDF) hollow fiber membrane having a pore size of 0.2 ⁇ m.
  • PVDF polyvinylidene fluoride
  • the system has a working pressure of -25 to -26 kPa, an operating temperature of 15 to 40 °C, and a pH of 5 to 9.
  • Step 3 Desalting the reverse osmosis system:
  • the primary reclaimed water obtained by the MBR system passes through the shut-off valve 41 and the water supply pump. , shut-off valve 43, safety filter 44 and membrane system high pressure pump 45 enter the reverse osmosis membrane system 46 in the filtration separation, dialysis water shut-off valve 47 stored in the reclaimed water tank 48 In the middle, high purity recycled water is obtained.
  • the membrane module of the reverse osmosis system is a reverse osmosis membrane module having a rejection of 98% sodium chloride.
  • the working conditions of the reverse osmosis system are: 25 to 35 ° C, the working pressure is 10 to 13.5 kPa, and the membrane flux is 20 mL/cm 2 .
  • the recovery rate of sewage is 80%, and the water quality of high-purity reclaimed water is shown in Table 4.
  • Table 4 Water quality of high-purity reclaimed water project concentration project concentration pH value 7.2 Conductivity ⁇ 200 ⁇ S/cm Turbidity ⁇ 1 chloride ⁇ 5 mg/L Chroma ⁇ 2 times (dilution factor) Total iron ⁇ 0.01mg/L COD Cr ⁇ 5mg/L manganese ⁇ 0.05mg/L SS (suspended matter) not detected Free chlorine ⁇ 0.1mg/L Total alkalinity ⁇ 30mg/L (based on calcium carbonate hardness) total hardness ⁇ 10mg/L (based on calcium carbonate hardness)
  • the water quality of the sewage is shown in Table 5.
  • Step 1 Electrolysis: The water supply pump 12 is started, and the sewage enters the electrolysis machine 13 through the shut-off valve 11 at a flow rate of 150 m 3 /h for electrolysis.
  • the working voltage of the electrolysis is 48V, the voltage between the two poles is 5.5 to 8.0 V, and the current density is 190 mA/cm 2 .
  • the nascent chlorine [Cl], hydroxyl [OH] and nascent Strong oxidizing substances such as oxygen [O] can kill plankton and bacteria in sewage, and can open or break macromolecules in sewage, and decompose macroscopic substances that are difficult to biodegrade into small molecular substances.
  • Step 2 MBR system filtration separation: the purified sewage after electrolysis passes through the grid 21 The solid impurities and colloids of the larger particles generated by electrolysis in the sewage are removed by filtration, and then enter the MBR reaction tank 26, and the blower 24 and the aerator 25 are activated. After the aeration is oxidized, the water pump is started. Under negative pressure, water molecules are separated by the MBR membrane module 23 to obtain dialysis water, and the dialyzed water is collected into the primary reclaimed water storage tank 29.
  • the membrane material of the MBR system is a polypropylene (PP) hollow fiber membrane having a pore size of 0.2 ⁇ m.
  • MBR polypropylene
  • the system has a working pressure of -20 to -23 kPa, an operating temperature of 5 to 45 °C, and a pH of 5 to 9.
  • Step 3 Desalting the reverse osmosis system:
  • the primary reclaimed water obtained by the MBR system passes through the shut-off valve 41 and the water supply pump. , shut-off valve 43, safety filter 44 and membrane system high pressure pump 45 enter the reverse osmosis membrane system 46 in the filtration separation, dialysis water shut-off valve 47 stored in the reclaimed water tank 48 In the middle, high purity recycled water is obtained.
  • the membrane module of the reverse osmosis system is a reverse osmosis membrane module having a rejection of 98% sodium chloride.
  • the working conditions of the reverse osmosis system are: 25 to 35 ° C, the working pressure is 20 to 25 kPa, and the membrane flux is 20 mL/cm 2 .
  • the recovery rate of sewage is 75%, and the water quality of high-purity reclaimed water is shown in Table 7.
  • Table 7 Water quality of high purity reclaimed water project concentration project concentration pH value 7.1 Conductivity ⁇ 176 ⁇ S/cm Turbidity ⁇ 1 chloride ⁇ 10 mg/L Chroma 1 Total iron ⁇ 0.05mg/L COD Cr ⁇ 6mg/L manganese ⁇ 0.01mg/L SS (suspended matter) not detected Free chlorine ⁇ 0.1mg/L Total alkalinity ⁇ 20mg/L (based on calcium carbonate hardness) total hardness ⁇ 10mg/L (based on calcium carbonate hardness)
  • the technical scheme of the invention can overcome the defects that the quality of the reclaimed water in the existing sewage regeneration technology is poor, and it is difficult to meet the water quality requirements of the production process of the industrial production, and the defects of large investment, high operating cost and secondary pollution to the environment can reduce sewage discharge. High water utilization efficiency and good industrial applicability.

Description

一种基于电解和双膜技术的再生水制造装置及其方法 技术领域
本发明涉及一种高纯再生水制造装置及其方法，特别是涉及一种电解技术与双膜技术结合的高纯再生水制造装置及其方法。
背景技术
水资源与环境污染问题日益受到人类社会的重视，一方面淡水用量不断增加，水资源日益紧缺，另一方面污水排放量日益增多，对环境污染日益严重，因此，污水处理和再生资源化循环利用越来越受到各国的重视。中国是一个水资源严重缺乏的国家，人均淡水资源占有量仅为世界平均水平的四分之一，是世界上最缺水的 13 个国家之一，目前，在全国 600 多座城市中，有 400 多座城市缺水，因此污水再生循环利用成为解决淡水资源不足的关键。但是，我国当前的污水处理多为达标排放，成熟的污水再生循环利用技术不多，应用到工程实践的更是少之又少，每天都有大量的污水经过处理达标后就直接排入江河、湖泊、海域，既造成了水资源的浪费又污染了环境，长此以往必将造成水资源的不可持续发展。据介绍，在我国城市水资源总消耗中，工业用水大约占 2/3 ，如将污水经过再生处理后用于工业用水，在节水方面将有很大的潜力，等于增加了 2/3 的淡水资源总量。
近年来，我国环境工作者在污水处理，再生循环利用方面作了大量工作，中国专利CN200410024576.8公开了'一种污水抽取再生水的工艺和专用设备'，它是将污水经过酶处理后，再经过滤和臭氧消毒而生产再生水的方法。中国专利CN101108760B公开了经过生化处理后达到排放标准的污水经过连续微滤处理的再生水循环利用方法，它是将生化出水的尾水作为源水，经过旋流混凝反应池、平流多斗沉淀池物化沉淀后进入中间水池，由提升泵送至连续微滤系统进行深度处理而生产再生水的方法。尽管污水再生的方法已有不少，各级政府和广大环境工作者在污水再生循环利用方面也做了大量的工作，但是污水回用量在工业用水中所占比例却不到2%，污水回用的领域也只限于对水质要求不高的行业，如工业冲渣除尘水、冷却水、企业内部绿化、冲厕等杂用，在水质要求较高的生产工艺用水方面则尝试很少。分析其原因，主要因为污水在工业上的循环利用存在如下问题：1、再生水质量不高：首先表现在现有的污水净化再生技术难以去除污水中的残留色度和臭味，再生水中还残留有各种营养物质和细菌、霉菌、藻类等，遇到适宜的温度、光照条件即会迅速繁殖导致水体发黑发臭，并产生难以处理的生物垢，对工艺设备也会造成不良影响，使再生水在工业生产中应用受到很大局限；其次是污水中总溶解盐含量高，并含有大量可以形成水垢的钙镁盐类物质，当其通过管道被输送到用水工艺设备时，会因长期的电化学腐蚀作用，使用水设备受到损坏，随着水中钙镁盐类在用水设备中不断地循环浓缩，进一步形成水垢，会导致用水设备阻塞。2、经济上不合算：生化后经过多级膜处理，虽然能够实现污水再生，但是一次性设备投资大，运行成本高于现行自来水价，从经济合算的标准衡量，仍然不尽如人意，再生水处理循环利用无法实现规模化。3、 二次污染：传统的再生水回用技术在对污水的净化过程中通常采用加入絮凝剂和杀菌剂对水中微生物、胶体物、固体颗粒进行沉淀后，再经过砂滤过滤、多介质过滤和膜过滤的净化工艺，其缺点是处理过程中要加入絮凝剂和消毒杀菌剂，不仅投资大、运行成本较高，而且加入的絮凝剂和杀菌剂还对环境造成不同程度的污染。由以上问题可知，研究开发适合中国经济现状和发展水平的安全、可靠、高效、低能耗、低投资、低成本的再生水循环利用技术和配套设备，为再生水回用的规模化、产业化发展奠定坚实的基础成为一项迫在眉睫的任务。
 技术问题
本发明的目的在于针对现有污水再生循环利用技术存在的问题，提供一种可克服现有污水再生技术中再生水质量较差、难以满足工业生产的生产工艺用水水质要求，且投资大、运行成本高和对环境产生二次污染等缺陷，可减少污水排放，提高水的利用效率的 基于电解和双膜技术的再生水制造装置 。
本发明的另一目的在于提供一种基于电解和双膜技术的再生水制造方法。
 技术解决方案
本发明是将工业污水和城市生活污水经过生化处理后达到排放标准的污水（称之为生化出水或深度处理排放污水）进行深度净化处理的生产高纯再生水制造装置及方法。
本发明所述基于电解和双膜技术的再生水制造装置设有电解系统、膜生物反应器系统（以下简称为MBR系统）和反渗透系统；
所述电解系统用于对深度处理排放污水进行电解处理，电解系统设有截止阀、供水泵和电解机；截止阀的进口外接生化出水排出口，供水泵的进口接截止阀的出口，供水泵的出口接电解机的进口，电解机的出口与MBR系统的进水口联接；
所述电解机设有电源和电解槽，电解槽内的阳极材料为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、金属的合金和纳米催化惰性阳极等中的一种；所述纳米催化惰性阳极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性阳极的基板可为钛板或塑料板等，这种电极具有较高的电催化反应活性，可以大幅度降低电解的过电位，减少副反应的发生。
所述MBR系统用于将电解系统所得净化污水进行进一步处理，MBR系统设有截止阀、格栅、MBR反应池、MBR膜组件、鼓风机、曝气器、排污泵、出水泵、初级再生水贮罐和MBR清洗系统；所述截止阀的进口接电解系统的电解机的出口，截止阀出口接格栅的进口，格栅的出口接MBR反应池的进口，MBR膜组件浸没在MBR反应池内，通过鼓风机及分布的曝气器对其进行曝气，MBR反应池的滤液（水）出口接出水泵的进口，出水泵的出口接初级再生水贮罐的进口，初级再生水贮罐收集到的滤液（水）用于进一步经过反渗透系统脱盐得供生产上循环利用的高纯再生水，MBR反应池的污泥出口接排污泵的进口，少量污泥经过排污泵抽吸排放；所述MBR膜组件可选自聚偏氟乙烯（PVDF）中空纤维膜、聚丙烯（PP）中空纤维膜、聚砜（PS）中空纤维膜、聚醚砜（PES）、聚丙烯腈（PAN）和聚氯乙烯（PVC）中空纤维膜等中的一种，所述MBR膜组件的膜孔径可为0.10～0.2μm，能高效进行固液分离，工作压力为-1～-50kPa，工作温度为5～45℃，适用pH为1～14，出水固定悬浮物可降至1mg/L，浊度可降至1NTU以下。该系统可彻底去除污水中的细菌和大肠杆菌，出水的大肠菌群为0，而菌落总数低于1CFU/mL；所述MBR清洗系统用于清洗MBR膜组件，MBR清洗系统设有清洗液罐、反冲洗泵和截止阀；清洗液罐的出口接反冲洗泵的进口，反冲洗泵的出口接截止阀的进口，截止阀的出口接MBR系统。
所述反渗透系统用于将MBR系统处理所得的初级再生水过滤、分离，得透析水（再生水）和浓缩水。反渗透膜系统设有截止阀、供水泵、保安过滤器、高压泵、反渗透膜组件和再生水贮罐。截止阀的进口接MBR系统的初级再生水贮罐的净化污水出口，截止阀的出口依次经供水泵、保安过滤器和高压泵进入反渗透膜组件，反渗透膜组件的透析水出口接再生水贮罐的进口。反渗透系统将MBR系统所得初级再生水经保安过滤器后用高压泵泵入反渗透系统，经反渗透膜过滤分离得透析水（再生水）和浓缩水，透析水进入贮罐得高纯再生水；浓缩水一部分经过浓缩水增压泵回流进行循环膜过滤分离，一部分回流进入电解工序循环使用，多余部分排放；
所述反渗透系统还包括反渗透浓缩液回收系统，反渗透浓缩液膜回收系统用于将反渗透膜过滤的浓缩水进行回收利用的系统，反渗透浓缩液回收系统设有回流浓缩水增压泵、阀门和截止阀，回流浓缩水增压泵入口接反渗透系统的浓缩水出口，回流浓缩水增压泵出口接反渗透过滤膜系统，反渗透过滤膜系统的浓缩水出口另一路回流接电解系统重复利用。
所述反渗透系统还包括一个反渗透膜清洗再生系统，反渗透膜清洗再生系统用于清洗反渗透过滤膜系统，反渗透膜清洗再生系统设有清洗液罐、反冲洗泵和截止阀，清洗液罐的进口经截止阀接反渗透过滤膜系统透析水出口，清洗液罐的一路出口接反渗透系统浓缩水出口，清洗液罐的另一路出口经反冲洗泵接供水泵出口。
本发明所述基于电解和双膜技术的再生水制造方法包括以下步骤：
1）电解：将生化出水经水泵提取后，输入电解机中进行电解，再经过格栅进入MBR系统，除去污水中被电解杀灭的浮游生物尸体、细菌及因电解产生的大颗粒固体杂质、胶体物质得净化污水；
在步骤1）中，所述生化出水是指污水经过生化处理达到GB 18918-2002《城镇污水处理厂污染物排放标准》三级排放标准的污水，其COD Cr≤120mg/L，BOD5≤60 mg/L ，SS≤50mg/L，色度≤50 ，动植物油≤20mg/L，石油类≤15mg/L，阴离子表面活性剂≤5 mg/L，氨氮≤25mg/L，总磷≤5 mg/L，电导率小于1500μs/cm；所述电解是将生化出水经过电解使之生成初生态的氯[Cl]、羟基[OH]和初生态的氧[O]，用以氧化分解污水中的动植物油、石油类、阴离子表面活性剂、有色物质等有机物和氨氮，并杀灭污水中微生物，同时，在电场作用下使污水中的悬浮物、胶体、带电微粒凝聚形成较大颗粒；所述电解的电解槽的工作电压可为2～250V，相邻两个电极间的电压可为2～18V，相邻两个电极间的最佳电压为3～8V，电流密度可为10～300mA/cm2，最佳为电流密度为50～210mA/cm2，生化出水经过电解后经阀门进入MBR系统。
2）MBR系统过滤：将经过电解系统处理所得的净化污水经管道流入MBR系统，进行MBR系统处理分离得初级再生水；
在步骤2）中，所述MBR系统是膜分离技术与生物技术有机结合的新型废水处理技术，它利用膜分离设备将生化反应池中的活性污泥和大分子有机物质进行截留，具有适应性强、生化效率高、抗负荷冲击能力强、占地面积小、处理效果好等优势。
3）反渗透脱盐：将经过MBR系统过滤所得的初级再生水经过高压泵泵入反渗透系统，经反渗透膜过滤脱盐，分离得透析水和浓缩水，透析水进入贮罐得高纯再生水。
在步骤3）中，所述反渗透系统的工作条件是：常温～45℃，工作压力为5～35kPa；反渗透系统的反渗透膜为对氯化钠截留率为98%的反渗透膜，膜组件的结构为卷式膜组件或管式膜组件，膜材料为醋酸纤维膜或复合膜，膜材料的截留分子量可为50～200MWCO。
本发明的技术方案为：生化处理后污水→电解→MBR系统→反渗透系统→高纯再生水。该高纯再生水水质良好，各项指标远优于GB/T19923-2005《城市污水再生利用 工业用水水质》标准，可作为各种行业的工业的生产工艺用水，即直接应用到工业的生产各工序中，达到清洁生产的目的。
 有益效果
采用该技术路线解决了现有污水回用技术难题，具有如下优势：
1、本发明采用电解的方法，具有如下突出效果：（1）在电流作用下电解使使残留于污水中的大分子开环或断链，增强污水的可生化性；（2）电解产生的初生态的氯[Cl]、羟基[OH]和初生态的氧[O]并氧化分解有机物，快速降低CODCr；（3）氧化分解污水中的氨氮，使残留氨氮进一步氧化，氨氮的脱除率可达80～90%，同时消除水中臭味。（4）大幅度降低污水的色度，经过了生化、物化等多种方法处理后二沉池出水的色度在80～300之间，一般的处理方法很难进一步脱除色度，经过电解可以将污水的色度从80～300之间降低到16～32。（5）使污水中的悬浮物、胶体、带电微粒在电场作用下凝聚形成较大颗粒后，经过后续的MBR系统过滤去除得净化污水。（6）污水中的重金属离子向电解机电解槽的阴极移动，在阴极形成沉淀，从而降低污水中的重金属离子含量。
2、降低污水COD总排放量，大幅提高污水可生化性：传统的生化末端加膜过滤技术，虽然可以实现部分中水回用，但不能降低污水COD的总排放量，本发明电解产生的初生态的氯[Cl]、羟基[OH]和初生态的氧[O]使残留于污水中的大分子开环或断链并迅速氧化分解有机物，不但大幅度降低污水COD的总排放量，而且提高污水的可生化性。
3、回用水率高、成本低：污水的回用率高达70%～90%，排放污水少，能耗低，高纯再生水生产成本低于1元/吨，远低于现行自来水价。
4、回用水质高：采用该技术路线产生的高纯再生水无色、无味，水质主要指标如表1，可以满足各种行业工业用水的水质要求。
表 1 高纯再生水水质指标
项目 浓度 项目 浓度
pH 值 6.5~8.5 电导率 ≤ 300μS/cm
浊度 ≤ 1 氯化物 ≤ 50 mg/L
色度 ≤ 3 倍（稀释倍数） 总铁 ≤ 0.05mg/L
CODCr ≤ 10mg/L 锰 ≤ 0.1mg/L
SS （悬浮物） ≤ 2mg/L 游离氯 ≤ 0.1mg/L
总碱度 ≤ 50mg/L
（ 以碳酸钙硬度计 ）		 总硬度 ≤ 10mg/L
（ 以碳酸钙硬度计 ）
5、脱色效果好：电解产生的初生态的氯[Cl]、羟基[OH]、初生态的氧[O]等强氧化性物质可使污水中的发色基团、助色基团氧转化为无色基团，使偶氮键破裂、大分子分解为小分子、硝基化合物还原为胺基化合物，达到脱色的目的。
6、不产生二次污染：采用电解技术处理生化出水的工艺替代物化处理工艺，不用加入絮凝剂、脱色剂和气浮剂等化学物质，不仅节省成本，而且节约物质消耗和不产生二次污染。
7、污泥产率低、排泥量少：采用本发明处理污水时，在二沉池出水后采用电解技术替代物化工艺，不用加入絮凝剂、脱色剂等化学物质，大幅度减少了污泥量，污泥量只有传统技术的二分之一。
8、构筑物少，固定资产投资省，设备少，占地少，维护方便：由于MBR膜的分离作用，膜组件直接安放在生化池内，不必设立沉淀、过滤等其他固液分离设备，不需要沉淀槽、石英沙过滤罐、活性碳吸附罐，固定资产投资少；另一方面反渗透系统由进口膜组件叠合而成，设备结构紧凑，占地面积省，生产工艺流程短，维护方便。
9、运行能耗低：MBR系统利用膜分离设备将生化反应池中的活性污泥和大分子有机物质进行截留，具有生化效率高，抗负荷冲击能力强，操作压力低，而反渗透系统单位产水量高，去除杂质彻底，能量消耗少，设备运行时能耗大幅度下降。
 附图说明
图 1 为本发明所述 基于电解和双膜技术的再生水制造装置 实施例的结构组成示意图。
本发明的最佳实施方式
本发明是在对现有污水处理厂生化出水的成份、性质和现有处理方案进行深入系统的对比研究之后完成的对生化出水的净化和再生循环利用工艺的设计，通过电解、 MBR 系统、反渗透系统等工艺的组合运用，从而形成一种 高纯再生水的制造装置及其 方法。
下面实施例将结合附图对本发明作进一步的说明。
参见图 1 ，本发明所述一种 基于电解和双膜技术的高纯再生水制造装置及其方法实施例 设有：
电解系统：电解系统用于电解处理，电解系统设有截止阀 11 、供水泵 12 和电解机 13 。截止阀 11 的进口外接生化出水排出口，供水泵 12 的进口接截止阀 11 的出口，供水泵 12 的出口接电解机 13 的进口，电解机 13 的出口与 MBR 系统的进水口联接。
MBR 系统： MBR 系统用于将电解系统所得净化污水进行进一步处理。 MBR 系统设截止阀 21 、格栅 22 、 MBR 膜组件 23 、鼓风机 24 、曝气器 25 、 MBR 反应池 26 、排污泵 27 、出水泵 28 和初级再生水贮罐 29 。截止阀 21 的进口接电解机 13 的出口，截止阀 21 的出口接格栅 22 的进口，格栅 22 的出口依次经过 MBR 反应池 26 、出水泵 28 进入初级再生水贮罐 29 。
MBR 清洗系统： MBR 清洗系统用于清洗 MBR 系统，设有清洗液罐 31 、反冲洗泵 32 和截止阀 33 。清洗液罐 31 的出口接反冲洗泵 32 的进口，反冲洗泵 32 的出口接截止阀 33 的进口，截止阀 33 的出口接 MBR 反应池 23 的出口。
反渗透系统：反渗透系统用于将 MBR 系统处理所得的初级再生水过滤、分离得透析水和浓缩水。反渗透系统设有截止阀 41 、供水泵 42 、截止阀 43 、保安过滤器 44 、膜系统高压泵 45 、反渗透过滤膜系统 46 、截止阀 47 和再生水贮罐 48 。截止阀 41 的进口接 MBR 系统初级再生水贮罐 28 的出口，截止阀 41 的出口依次经供水泵 42 、截止阀 43 、保安过滤器 44 和膜系统高压泵 45 进入反渗透过滤膜系统 46 ，反渗透过滤膜系统 46 的透析水出口经截止阀 47 接再生水贮罐 48 的进口。
反渗透浓缩液回收系统：反渗透浓缩液回收系统是用于将反渗透膜过滤浓缩水进行回用的系统。反渗透过滤膜回收系统设有回流浓缩水增压泵 51 、阀门 52 、截止阀 53 和阀门 54 。回流浓缩水增压泵 51 的进口接反渗透过滤膜系统 46 的浓缩水出口，回流浓缩水增压泵 51 的出口接反渗透过滤膜系统 46 的进口；反渗透过滤膜系统 46 的浓缩水出口另一路经阀门 52 、截止阀 53 、阀门 54 回流接电解机 13 重复利用。
反渗透膜清洗再生系统：反渗透膜清洗再生系统用于清洗反渗透过滤膜系统，反渗透膜清洗再生系统设有截止阀61、清洗液罐 62、截止阀63、截止阀64、反冲洗泵65和截止阀66。清洗液罐62的进口经截止阀61接反渗透过滤膜系统46透析水出口，清洗液罐62的一路出口经截止阀63、阀门52接反渗透过滤膜系统46浓缩水出口，清洗液罐62的另一路出口经截止阀64后，一路经反冲洗泵65和截止阀 66接供水泵42出口。
 本发明的实施方式
以下结合图 1 给出 基于电解和双膜技术的再生水制造方法 的具体实施例。
实施例 1
500 吨 / 日污水的深度净化再生及循环利用 工程。
所述污水的水质情况如表 2 所示。
表 2 污水的水质情况
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 56 5 浊度 NTU 19
2 BOD5 mg/L 7 6 色度 倍 60
3 SS mg/L 13 7 pH 7.3
4 NH3-N mg/L 23 8 电导率 µS/cm 410
步骤 1 、电解：起动供水泵 12 ，污水以 25 ｍ3 /h 流速经截止阀 11 进入电解机 13 进行电解。所述电解的工作电压为 12V ，两极间的电压为了 3.5 ～ 8.0V ，电流密度 130mA/cm2 ，在电流作用下，电解产生的初生态的氯 [Cl] 、羟基 [OH] 和初生态的氧 [O] 等强氧化性物质，既可以杀灭污水中的浮游生物、细菌，又可以使污水中的大分子物质开环或断链，使难生物降解的大分子物质分解为小分子物质，增加 BOD5/CODCr 比值，提高污水的可生化性；同时，氧化分解污水中的高分子有机物、氨氮、有色基团、助色基团等，并使污水中的悬浮物、胶体、带电微粒在电场作用下形成较大颗粒，经过后续的 MBR 系统过滤分离去除而净化污水，电解系统处理后净化污水的各项水质指标如表 3 。
表 3 电解后的净化污水水质情况
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 43 5 浊度 NTU 9
2 BOD5 mg/L 19 6 色度 倍 4
3 SS mg/L 33 7 pH 7.4
4 NH3-N mg/L 3 8 电导率 µS/cm 410
步骤 2 、 MBR 系统过滤分离：电解后的净化污水再经过格栅 21 过滤除去污水中因电解产生的较大颗粒的固体杂质、胶体后进入 MBR 反应池 26 中，启动鼓风机 24 和曝气器 25 ，污水经过曝气氧化后，启动出水泵 28 ，在负压作用下，水分子透过 MBR 膜组件 23 分离，得透析水，透析水收集到初级再生水贮罐 29 中。
所述 MBR 系统的膜材料为孔径 0.2 微米的聚偏氟乙烯（ PVDF ）中空纤维膜。 MBR 系统分离的工作压力为 -25 ～ -26 kPa ，工作温度为 15 ～ 40 ℃， pH 为 5 ～ 9 。
步骤 3 、反渗透系统脱盐： MBR 系统所得初级再生水再依次经截止阀 41 、供水泵 42 、截止阀 43 、保安过滤器 44 和膜系统高压泵 45 进入反渗透过滤膜系统 46 中过滤分离，透析水截止阀 47 贮存于再生水贮罐 48 中，得到高纯再生水。
所述反渗透系统的膜组件为对氯化钠截留率为 98% 的反渗透卷式膜组件。反渗透系统的工作条件是： 25 ～ 35℃ ，工作压力为 10 ～ 13.5 kPa ，膜通量为 20mL/cm2 。污水的回收率为 80% ，高纯再生水的水质情况如表 4 所示。
表 4 高纯再生水的水质情况
项目 浓度 项目 浓度
pH 值 7.2 电导率 ≤ 200 μ S/cm
浊度 ≤ 1 氯化物 ≤ 5 mg/L
色度 ≤ 2 倍（稀释倍数） 总铁 ≤ 0.01mg/L
CODCr ≤ 5mg/L 锰 ≤ 0.05mg/L
SS （悬浮物） 未检出 游离氯 ≤ 0.1mg/L
总碱度 ≤ 30mg/L
（ 以碳酸钙硬度计 ）		 总硬度 ≤ 10mg/L
（ 以碳酸钙硬度计 ）
实施例 2
3000 吨 / 日污水的深度净化再生及循环利用 工程。
所述污水的水质情况如表 5 所示。
表 5 污水的水质情况
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 116 5 浊度 NTU 15
2 BOD5 mg/L 16 6 色度 倍 80
3 SS mg/L 23 7 pH 7.7
4 NH3-N mg/L 16 8 电导率 µS/cm 560
步骤 1 、电解：起动供水泵 12 ，污水以 150 ｍ 3 /h 流速经截止阀 11 进入电解机 13 进行电解。所述电解的工作电压为 48V ，两极间的电压为 5.5 ～ 8.0 V ，电流密度 190mA/cm2 ，在电流作用下，电解产生的初生态的氯 [Cl] 、羟基 [OH] 和初生态的氧 [O] 等强氧化性物质，既可以杀灭污水中的浮游生物、细菌，又可以使污水中的大分子物质开环或断链，使难生物降解的大分子物质分解为小分子物质，增加 BOD5/CODCr 比值，提高污水的可生化性；同时，氧化分解废水中的高分子有机物、氨氮、有色基团和助色基团等，并使废水中的悬浮物、胶体、带电微粒在电场作用下形成较大颗粒，经过后续的 MBR 系统过滤分离去除而达到净化污水的效果，电解系统处理后净化污水的各项水质指标如表 6 。
表 6 电解后的净化污水水质情况
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 81 5 浊度 NTU 7
2 BOD5 mg/L 43 6 色度 倍 8
3 SS mg/L 35 7 pH 7.8
4 NH3-N mg/L 2 8 电导率 µS/cm 560
步骤 2 、 MBR 系统过滤分离：电解后的净化污水再经过格栅 21 过滤除去污水中因电解产生的较大颗粒的固体杂质、胶体后进入 MBR 反应池 26 中，启动鼓风机 24 和曝气器 25 ，污水经过曝气氧化后，启动出水泵 28 ，在负压作用下，水分子透过 MBR 膜组件 23 分离，得透析水，透析水收集到初级再生水贮罐 29 中。
所述 MBR 系统的为膜材料为孔径 0.2 微米的聚丙烯（ PP ）中空纤维膜。 MBR 系统分离的工作压力为 -20 ～ -23 kPa ，工作温度为 5 ～ 45 ℃， pH 为 5 ～ 9 。
步骤 3 、反渗透系统脱盐： MBR 系统所得初级再生水再依次经截止阀 41 、供水泵 42 、截止阀 43 、保安过滤器 44 和膜系统高压泵 45 进入反渗透过滤膜系统 46 中过滤分离，透析水截止阀 47 贮存于再生水贮罐 48 中，得到高纯再生水。
所述反渗透系统的膜组件为对氯化钠截留率为 98% 的反渗透卷式膜组件。反渗透系统的工作条件是： 25 ～ 35℃ ，工作压力为 20 ～ 25 kPa ，膜通量为 20mL/cm2 。污水的回收率为 75% ，高纯再生水的水质情况如表 7 所示。
表 7 高纯再生水的水质情况
项目 浓度 项目 浓度
pH 值 7.1 电导率 ≤ 176 μ S/cm
浊度 ≤ 1 氯化物 ≤ 10 mg/L
色度 1 总铁 ≤ 0.05mg/L
CODCr ≤ 6mg/L 锰 ≤ 0.01mg/L
SS （悬浮物） 未检出 游离氯 ≤ 0.1mg/L
总碱度 ≤ 20mg/L
（ 以碳酸钙硬度计 ）		 总硬度 ≤ 10mg/L
（ 以碳酸钙硬度计 ）
工业实用性
本发明的技术方案可克服现有污水再生技术中再生水质量较差、难以满足工业生产的生产工艺用水水质要求，且投资大、运行成本高和对环境产生二次污染等缺陷，可减少污水排放，高水的利用效率，具备良好的工业实用性。
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Claims (10)

  1. 一种基于电解和双膜技术的再生水制造装置，其特征在于设有电解系统、MBR系统和反渗透系统；
    所述电解系统用于对深度处理排放污水进行电解处理，电解系统设有截止阀、供水泵和电解机；截止阀的进口外接生化出水排出口，供水泵的进口接截止阀的出口，供水泵的出口接电解机的进口，电解机的出口与MBR系统的进水口联接；所述电解机设有电源和电解槽；
    所述MBR系统用于将电解系统所得净化污水进行进一步处理，MBR系统设有截止阀、格栅、MBR反应池、MBR膜组件、鼓风机、曝气器、排污泵、出水泵、初级再生水贮罐和MBR清洗系统；所述截止阀的进口接电解系统的电解机的出口，截止阀出口接格栅的进口，格栅的出口接MBR反应池的进口，MBR膜组件浸没在MBR反应池内，通过鼓风机及分布的曝气器对其进行曝气，MBR反应池的滤液出口接出水泵的进口，出水泵的出口接初级再生水贮罐的进口，MBR反应池的污泥出口接排污泵的进口，污泥经过排污泵抽吸排放；
    所述反渗透系统用于将MBR系统处理所得的初级再生水过滤、分离，得透析水和浓缩水，反渗透膜系统设有截止阀、供水泵、保安过滤器、高压泵、反渗透膜组件和再生水贮罐，截止阀的进口接MBR系统的初级再生水贮罐的净化污水出口，截止阀的出口依次经供水泵、保安过滤器和高压泵进入反渗透膜组件，反渗透膜组件的透析水出口接再生水贮罐的进口，反渗透系统将MBR系统所得初级再生水经保安过滤器后用高压泵泵入反渗透系统，经反渗透膜过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分经过浓缩水增压泵回流进行循环膜过滤分离，一部分回流进入电解工序循环使用，多余部分排放；
    所述反渗透系统还包括反渗透浓缩液回收系统，反渗透浓缩液膜回收系统用于将反渗透膜过滤的浓缩水进行回收利用的系统，反渗透浓缩液回收系统设有回流浓缩水增压泵、阀门和截止阀，回流浓缩水增压泵入口接反渗透系统的浓缩水出口，回流浓缩水增压泵出口接反渗透过滤膜系统，反渗透过滤膜系统的浓缩水出口另一路回流接电解系统重复利用；
    所述反渗透系统还包括一个反渗透膜清洗再生系统，反渗透膜清洗再生系统用于清洗反渗透过滤膜系统，反渗透膜清洗再生系统设有清洗液罐、反冲洗泵和截止阀，清洗液罐的进口经截止阀接反渗透过滤膜系统透析水出口，清洗液罐的一路出口接反渗透系统浓缩水出口，清洗液罐的另一路出口经反冲洗泵接供水泵出口。
  2. 如权利要求1所述的一种基于电解和双膜技术的再生水制造装置，其特征在于所述电解槽内的阳极材料为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、金属的合金和纳米催化惰性阳极中的一种。
  3. 如权利要求2所述的一种基于电解和双膜技术的再生水制造装置，其特征在于所述纳米催化惰性阳极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性阳极的基板为钛板或塑料板。
  4. 如权利要求1所述的一种基于电解和双膜技术的再生水制造装置，其特征在于所述MBR膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜、聚丙烯腈和聚氯乙烯中空纤维膜中的一种。
  5. 如权利要求4所述的一种基于电解和双膜技术的再生水制造装置，其特征在于所述MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃，pH为1～14。
  6. 如权利要求1所述的一种基于电解和双膜技术的再生水制造装置，其特征在于所述MBR清洗系统用于清洗MBR膜组件，MBR清洗系统设有清洗液罐、反冲洗泵和截止阀；清洗液罐的出口接反冲洗泵的进口，反冲洗泵的出口接截止阀的进口，截止阀的出口接MBR系统。
  7. 一种基于电解和双膜技术的再生水制造方法，其特征在于，使用如权利要求1所述一种基于电解和双膜技术的再生水制造装置，所述制造方法包括以下步骤：
    1）电解：将生化出水经水泵提取后，输入电解机中进行电解，再经过格栅进入MBR系统，除去污水中被电解杀灭的浮游生物尸体、细菌及因电解产生的大颗粒固体杂质、胶体物质得净化污水；
    2）MBR系统过滤：将经过电解系统处理所得的净化污水经管道流入MBR系统，进行MBR系统处理分离得初级再生水；
    3）反渗透脱盐：将经过MBR系统过滤所得的初级再生水经过高压泵泵入反渗透系统，经反渗透膜过滤脱盐，分离得透析水和浓缩水，透析水进入贮罐得高纯再生水。
  8. 如权利要求7所述的一种基于电解和双膜技术的再生水制造方法，其特征在于在步骤1）中，所述电解的电解槽的工作电压为2～250V，相邻两个电极间的电压为2～18V，电流密度为10～300mA/cm2。
  9. 如权利要求8所述的一种基于电解和双膜技术的再生水制造方法，其特征在于所述相邻两个电极间的电压为3～8V，电流密度为50～210mA/cm2。
  10. 如权利要求7所述的一种基于电解和双膜技术的再生水制造方法，其特征在于在步骤3）中，所述反渗透系统的工作条件是：常温～45℃，工作压力为5～35kPa；反渗透系统的反渗透膜为对氯化钠截留率为98%的反渗透膜，膜组件的结构为卷式膜组件或管式膜组件，膜材料为醋酸纤维膜或复合膜，膜材料的截留分子量为50～200MWCO。
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