WO2012171365A1 - Electrochemistry and electrodialysis-based apparatus and method for recycling wastewater from papermaking - Google Patents

Electrochemistry and electrodialysis-based apparatus and method for recycling wastewater from papermaking Download PDF

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WO2012171365A1
WO2012171365A1 PCT/CN2012/072025 CN2012072025W WO2012171365A1 WO 2012171365 A1 WO2012171365 A1 WO 2012171365A1 CN 2012072025 W CN2012072025 W CN 2012072025W WO 2012171365 A1 WO2012171365 A1 WO 2012171365A1
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electrodialysis
water
wastewater
ultrafiltration membrane
outlet
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PCT/CN2012/072025
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French (fr)
Chinese (zh)
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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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—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
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the invention relates to a papermaking wastewater treatment, in particular to a papermaking wastewater recycling device and method based on electrochemical and electrodialysis technology.
  • Pulp and papermaking wastewater refers to the cooking waste liquid (also known as black liquor, red liquor) produced by chemical pulping, the middle water produced during the washing and bleaching process, and the white water produced in the papermaking process.
  • the cooking waste liquid also known as black liquor, red liquor
  • 1 t of organic matter and 400 kg of alkali and sulfide are dissolved in black liquor
  • 1 t of sulfite pulp is produced with about 900 kg of organic matter and 200 kg of oxide (calcium, magnesium, etc.) and sulfide are dissolved in red.
  • the discharge of waste liquid into rivers not only seriously pollutes the water source, but also causes a large amount of waste of resources.
  • the paper industry is a traditional water user and one of the important sources of water pollution.
  • China's paper industry wastewater discharge and COD emissions rank first in all types of industrial emissions in China.
  • the paper industry has the most serious pollution to the water environment. It is not only the primary problem of pollution prevention and control in China's paper industry, but also the national industrial wastewater. The primary problem of compliance and water conservation.
  • China's county and county paper and paper products industrial wastewater discharge accounted for 18.6% of the country's total industrial emissions, of which treatment discharge standards accounted for 49.3% of the total discharge of paper industry wastewater, COD emissions from wastewater accounted for national industry 44.0% of total COD emissions. Therefore, how to eliminate the pollution of papermaking wastewater and make use of valuable resources in waste liquid is a work of great social and economic value, which should be taken seriously.
  • Papermaking wastewater has complex composition and poor biodegradability. It is a difficult industrial wastewater. Its sources and characteristics are:
  • the black liquor produced by alkaline pulping and the red liquor produced by acid pulping Most paper mills in China use alkaline pulping to produce black liquor.
  • the pollutants contained in the black liquor account for more than 90% of the total pollution discharge of the paper industry, and have high concentration and refractory characteristics. Its treatment has always been a major problem.
  • Lignin is a kind of non-toxic natural high-molecular substance. It has a wide range of uses as a chemical raw material, and polypentose can be used as livestock feed.
  • the mid-stage pulping wastewater refers to the wastewater discharged from the cooking slurry after black liquor extraction in the process of screening, washing and bleaching.
  • the color is dark yellow, accounting for 8% to 9% of the total pollution discharge of the paper industry.
  • the load is about 310kg.
  • the water concentration in the middle section is higher than that in domestic sewage.
  • the ratio of BOD to COD is between 0.20 and 0.35.
  • the biodegradability is poor, the organic matter is difficult to biodegrade and the treatment is difficult.
  • the organic matter in the middle water is mainly lignin, cellulose, organic acid, etc., mainly soluble COD.
  • the most serious environmental pollution is the chlorine-containing wastewater generated during the bleaching process, such as chlorinated bleaching wastewater and hypochlorite bleaching wastewater.
  • Hypochlorite bleaching wastewater mainly contains chloroform and contains more than 40 kinds of other organic chlorides, among which various chlorophenols are the most, such as dichlorophenol and trichlorophenol.
  • the bleaching waste liquid contains toxic dioxins, which are extremely toxic, posing a serious threat to the ecological environment and human health.
  • White water is the papermaking section wastewater, which comes from the papermaking process in the papermaking workshop.
  • White water mainly contains fine fibers, fillers, coatings and dissolved wood components, as well as added rubber compounds, wet strength agents, preservatives, etc., which are mainly insoluble COD, have low biodegradability, and have a certain preservative added. toxicity.
  • White water has a large amount of water, but its organic pollution load is much lower than that of cooking black liquor and middle-stage wastewater. Almost all paper mill paper mills now use partial or fully enclosed systems to reduce paper consumption, save power, increase white water reuse, and reduce excess white water emissions.
  • the methods used for papermaking wastewater treatment mainly include: physical filtration method, coagulation sedimentation method, adsorption method, advanced oxidation method, air floatation method, acid absorption method, catalytic oxidation method, biochemical method, etc., each method has Various advantages and disadvantages. Since the single treatment method is difficult to achieve the effect, in practical application, several methods are usually combined according to the actual situation of the wastewater to be treated.
  • the typical production process is to physically treat the papermaking wastewater through filtration and then flocculation and sedimentation. After the biochemical treatment, the standard is discharged.
  • Chinese patent CN1125696 discloses a method for treating and recycling papermaking wastewater, which is a physical-chemical method for preheating black liquor and bleaching wastewater under normal temperature and normal pressure conditions.
  • Treatment of separated straw pulp - acidification separation - neutralization The treatment process of acid-base separation and decolorization, the straw pulp, lignin and caustic soda in the wastewater are all recycled, and the treated water is used for cooking and bleaching. In the process of treatment, no secondary pollution occurs, and static measurement by computer is used.
  • the mixer has a small footprint, low investment, low operating cost, high efficiency, convenient installation and use, and is suitable for grass pulping enterprises other than the ammonium imide method.
  • Chinese patent CN101205107 discloses a method for treating and recycling papermaking wastewater, which mainly comprises steps of wet pulp recovery, coagulation sedimentation, three-phase anaerobic treatment, desulfurization, bio-iron treatment, filtration sterilization and recycling.
  • the invention firstly pretreats the papermaking wastewater, and then carries out the bio-iron treatment on the pre-treated effluent, so that the activated sludge forms a granular iron sludge with compact structure, small particle size, large specific surface area and good dehydration, and reused.
  • the A/O activated sludge treatment system carries out biochemical action, and the water for producing high-grade paper is further treated by micro-flocculation filtration technology to make the effluent water quality better.
  • the object of the present invention is to provide a lower cost for the existing papermaking wastewater treatment method, such as high cost, low efficiency, mostly treated wastewater, no deep treatment recycling, waste of water resources and the like.
  • a papermaking wastewater recycling device and method based on electrochemical and electrodialysis technology with high efficiency and recyclability.
  • the papermaking wastewater of the invention is a papermaking wastewater which has reached the discharge standard of discharge level III by the secondary settling tank after the conventional filtration, flocculation and biochemical treatment.
  • the papermaking wastewater recycling device based on electrochemical and electrodialysis technology of the invention has:
  • the nano catalytic electrolysis system has a shut-off valve, a water pump, a nano catalytic electrolysis machine, a buffer sedimentation tank and a filter; the inlet of the shut-off valve is externally connected to the discharge port of the second sedimentation tank of the papermaking wastewater, and the inlet of the water pump is connected to the outlet of the shut-off valve.
  • the outlet of the water pump is connected to the inlet of the nano catalytic electrolysis machine, the outlet of the nano catalytic electrolysis machine is connected with the inlet of the buffer sedimentation tank, and the outlet of the buffer sedimentation tank is connected through the inlet of the water pump and the filter;
  • Immersion ultrafiltration membrane filtration separation system immersion ultrafiltration membrane filtration separation system is used to filter and separate the purified wastewater obtained by the nano catalytic electrolysis system into dialysis water and concentrated water.
  • the immersion ultrafiltration membrane filtration separation system is provided with a shut-off valve.
  • the inlet of the shut-off valve is connected with the filter outlet of the nano catalytic electrolysis system through the inlet pipe, the shut-off valve
  • the outlet is connected to the immersion ultrafiltration membrane tank, and the ultrafiltration membrane is immersed in the printing and dyeing purification wastewater in the immersion ultrafiltration membrane tank, and the suction pump sucks the water negative pressure from the inner side of the ultrafiltration membrane through the membrane wall, and the generated dialysis water passes.
  • the suction pump collects the dialysis water storage tank for further desalination by electrodialysis to obtain recycled water for recycling in production.
  • the inlet of the shut-off valve is connected to the outlet of the precipitation tank of the nano catalytic electrolysis system, the outlet of the shut-off valve is connected to the inlet of the immersion ultrafiltration membrane tank, and the outlet of the immersion ultrafiltration membrane tank is sequentially passed through the suction pump and the shut-off valve into the dialysis water storage tank;
  • the ultrafiltration membrane cleaning system is used to clean the ultrafiltration membrane filtration separation system.
  • the ultrafiltration membrane cleaning system is provided with a cleaning liquid tank, a backwashing pump, a shut-off valve and a connecting pipe, and the outlet of the cleaning liquid tank is backwashed.
  • the inlet of the pump, the outlet of the backwashing pump is connected to the inlet of the shut-off valve, and the outlet of the shut-off valve is connected to the ultrafiltration membrane system;
  • Electrodialysis system is equipped with a shut-off valve, water supply pump, electrodialysis machine, dialysis water storage tank and concentrated water storage tank; the inlet of the shut-off valve is connected to the outlet of the dialysis water storage tank of the immersion ultrafiltration membrane filtration separation system.
  • the outlet of the valve is connected to the inlet of the water supply pump, the outlet of the water supply pump is connected to the inlet of the dialysis machine, the dialysis water outlet of the electrodialysis machine is connected to the dialysis water storage tank, and the concentrated water outlet of the electrodialysis is connected to the concentrated water storage tank.
  • the immersed ultrafiltration membrane filtration system can remove solid impurities, plankton, bacteria, colloids and the like in the waste water, and the immersion membrane adopts an external pressure open filtration design, and can be directly immersed in the waste water, so the system covers the area. small.
  • the working conditions are: normal temperature ⁇ 45 ° C, working pressure is 3 ⁇ 50 kPa.
  • the electrodialysis system may be selected from an inverted electrodialysis system (EDR), a liquid membrane electrodialysis system (EDLM), a filled electrodialysis system (EDI), a bipolar electrodialysis system (EDMB) or a stepless hydroelectric dialysis system.
  • EDR inverted electrodialysis system
  • EDLM liquid membrane electrodialysis system
  • EDI filled electrodialysis system
  • EDMB bipolar electrodialysis system
  • stepless hydroelectric dialysis system a stepless hydroelectric dialysis system.
  • the electrodialysis system can separate the dialysis water obtained by the immersion ultrafiltration membrane filtration separation system into dialysis water (desalted water) and concentrated water by electrodialysis to meet the quality requirements of different production process waters in industrial production.
  • the working conditions for electrodialysis are 0.5 to 3.0 kg/cm 2 , the operating voltage is 50 to 250 V, and the current intensity is 1 to 3 A.
  • the electrodialysis system can perform one-stage desalting, two-stage desalting or three-stage desalting according to the salt content in the wastewater, so that the salt content of the reclaimed water meets the process water requirement of industrial production, and the salt rejection rate can reach 45-80%.
  • the papermaking wastewater recycling method based on electrochemical and electrodialysis technology of the present invention comprises the following steps:
  • Nano-catalytic electrolysis After the papermaking wastewater is extracted by water pump, it is input into the nano-catalytic electrolysis machine for catalytic micro-electrolysis, and then input into a multi-media filter for filtration to remove waste water from the wastewater due to solid impurities, plankton, bacteria and colloids. , determine that its SDI should be less than 5;
  • the sodium chloride content of the papermaking wastewater may be 6 ⁇ 30 ⁇ , preferably 0.6 ⁇ to 1.3 ⁇ , and the sodium chloride content may be insufficient to add industrial sodium chloride to 6 ⁇ 50
  • the working voltage of the nano catalytic electrolysis can be 2 to 500 V, the voltage difference between the two plates is 2 to 18 V, the optimum voltage difference is 4 to 10 V, and the current density can be 5 to 300 mA/cm 2 .
  • the optimum current density is 50-200 mA/cm 2
  • the papermaking advanced treatment wastewater is electrolyzed to produce eutectic strong oxidizing substances, oxidative decomposition, oxidative decomposition of organic matter in wastewater, removal of color, flocculation and sedimentation of impurities, reduction of COD and killing Microbial
  • the nano-catalytic electrolysis is to subject the papermaking advanced treatment wastewater to nano-catalysis, and the residence time of the wastewater in the electrolysis tank is 2 to 4 minutes, and electrolysis is used to generate an initial ecological strong oxidizing substance for oxidative decomposition of organic matter in the wastewater.
  • the microorganisms in the wastewater are killed, and at the same time, suspended matter, colloids and charged particles in the wastewater are agglomerated to form larger particles under the action of an electric field; the filtration is one of sand filtration or multi-media filtration or microfiltration.
  • the wastewater obtained by catalytic electrolysis is subjected to sand filtration, multi-media filtration or microfiltration, and the obtained wastewater has a chromaticity of 1 to 6, a COD of 50 to 300 mg/L, an ammonia nitrogen of 0 to 10 mg/L, and an SS of 0 to 10 mg/L.
  • the papermaking advanced treatment wastewater refers to the treated wastewater after the papermaking wastewater is treated by the existing papermaking wastewater treatment method and facilities to reach the discharge standard of the third grade or above.
  • the working condition of the ultrafiltration system filtration treatment may be: normal temperature to 45 ° C, working pressure may be 3 to 50 kPa; the obtained dialysis water has a chromaticity of 1 to 3, and the COD is 20 to 100 mg / L, ammonia nitrogen is 0 to 1 mg/L, and SS is 0 to 1 mg/L.
  • Electrodialysis The dialysis water obtained by the immersion ultrafiltration filtration treatment of the step 2) is sent to an electrodialysis system by water pumping, and electrolyzed and desalted to obtain desalted water and concentrated water.
  • the color of the obtained desalinated water is 1-2, the COD is 10-50 mg/L, the ammonia nitrogen is not detected, the SS is not detected, and the total hardness is less than 350 mg/L.
  • the electrodialysis system may have an operating condition of 0.5 to 3.0 kg/cm2, an operating voltage of 50 to 250 V, and a current intensity of 1 to 3 A.
  • the invention not only overcomes the single-use membrane filtration separation treatment, but also overcomes the unsatisfactory wastewater treatment effect of the conventional papermaking wastewater method, and the waste water pollutes the environment, and can turn the decay into the spirit, change the waste into the resource, and the existing The papermaking process treats wastewater purification and recycling. Compared with the prior art, it has the following outstanding advantages:
  • Biochemical post-papermaking wastewater undergoes nano-catalytic electrolysis to further reduce COD.
  • the microorganisms such as bacteria remove the bio-contamination of the membrane, greatly reduce the number of membrane cleanings, reduce the cost of membrane cleaning and regeneration, increase the efficiency of membrane use, prolong the service life of the membrane, and reduce the cost of membrane replacement;
  • Partial desalination instead of reverse osmosis desalination by electrodialysis technology can not only make desalted water meet the technical requirements of papermaking process water, but also reduce electricity consumption, save energy and reduce cost;
  • the pre-ecologically strong oxidizing substances produced by nano-catalytic electrolysis kill the microorganisms in the wastewater, so that the microbial living organisms in the wastewater are reduced to less than 30/ml, and the microbial contamination of the membrane material is eliminated.
  • Heavy metal ions in the wastewater move toward the cathode of the electrolytic tank to form a precipitate at the cathode, thereby reducing the content of heavy metal ions in the wastewater.
  • FIG. 1 is a schematic structural view of an embodiment of a papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to the present invention.
  • the invention is a design of a process for purifying and recycling a papermaking wastewater after deep treatment after an in-depth systematic comparative study on the composition, properties and existing treatment schemes of the existing advanced treatment papermaking wastewater, which adopts nano catalytic electrolysis
  • FIG. 1 an embodiment of a papermaking wastewater recycling device based on electrochemical and electrodialysis technology of the present invention is provided with:
  • Nano Catalytic Electrolysis System is used for nano catalytic electrolysis, precipitation and other processing steps.
  • Nano catalytic electrolysis system with shut-off valve 11 Water supply pump 12 , nano catalytic electrolysis machine 13 , sedimentation tank 14 ; the inlet of the shut-off valve 11 is connected to the discharge port of the printing and dyeing wastewater (second settling tank), the inlet of the water supply pump 12 is connected to the outlet of the shut-off valve 11 , the water supply pump The outlet of 12 is connected to the inlet of the nano catalytic electrolysis machine 13, and the outlet of the nano catalytic electrolytic tank 13 is connected to the inlet of the precipitation tank 14.
  • Immersion ultrafiltration membrane filtration separation system is used for filtering and separating the printing and dyeing wastewater obtained by the nano catalytic electrolysis system to obtain dialysate (water) and concentrate (water).
  • the inlet is connected to the outlet of the precipitation tank 14 of the nano catalytic electrolysis system, the outlet of the shut-off valve 21 is connected to the inlet of the submerged ultrafiltration membrane tank 25, and the outlet of the submerged ultrafiltration membrane tank 25 is sequentially passed through the water pump 26 and the shut-off valve. 27 Enter the dialysate (water) tank 28 .
  • Ultrafiltration membrane cleaning system Ultrafiltration membrane cleaning system for cleaning ultrafiltration membrane filtration separation system, with cleaning fluid tank 31, backwash pump 32 , shut-off valve 33.
  • the outlet of the cleaning fluid 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 ultrafiltration membrane system 22 .
  • Electrodialysis system The electrodialysis system is provided with a shut-off valve 41, a water supply pump 42, an electrodialysis machine 43, a dialysate (water) storage tank 44, and a concentrate (water) storage tank 45.
  • the printing and dyeing wastewater obtained by the immersion ultrafiltration system enters the electrodialysis machine 43 through the shut-off valve 41 and the water supply pump 42, and the dialysate (water) outlet of the electrodialysis machine 43 is connected to the dialysate (water) storage tank 44, and the electrodialyzer 43 is concentrated.
  • the liquid (water) outlet is connected to a concentrate (water) storage tank 45.
  • Figure 1 The method for purifying and recycling the papermaking wastewater implemented by the papermaking wastewater recycling device based on the electrochemical and electrodialysis technology is shown.
  • Serial number project unit measured value Serial number project unit measured value 1 COD Cr Mg/L 186 4 Chroma 80 2 SS Mg/L 90 5 pH 7.5 3 Turbidity NTU 6 6 Conductivity ⁇ S/cm 3200
  • the nano-catalyzed electrolyzed water directly enters the precipitation tank 14 , and after sedimentation, it enters the immersion ultrafiltration membrane system to remove solid impurities, plankton, bacteria and colloids in the water to purify the wastewater.
  • the nano catalytic electrolysis has an operating voltage of 8 to 9 V and a current density of 50 mA/cm 2 , and the nascent chlorine [Cl], hydroxyl group and nascent oxygen [O] produced by nano catalytic electrolysis kills microorganisms in the wastewater,
  • the organic matter in the wastewater is oxidatively decomposed, and the suspended solids, colloids and charged particles in the wastewater are formed into larger particles under the action of an electric field, and then removed by an immersed ultrafiltration membrane filtration separation system to purify the wastewater, and the SDI is determined to be 1.9.
  • the purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation system passes through the shut-off valve 41 and the water supply pump 42 Entering the electrodialysis machine 43 for electrodialysis desalination, separating into dialysate (water) and concentrate, dialysate (water) passing through the dialysate (water) outlet and piping into the dialysate (water) storage tank 44
  • the concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
  • the electrodialysis system is an inverted electrodialysis system (EDR), and the working conditions of electrodialysis are an operating voltage of 0.5 kg/cm 2 , an operating voltage of 50 to 250 V, and a current intensity of 1 to 3 A.
  • EDR inverted electrodialysis system
  • the flow rates of the dialysate and concentrate are 6.5T/h and 1.0T/h, respectively, and the recovery rate of wastewater is 86.7%.
  • the quality of recycled water is shown in Table 2, and the indicators of concentrated wastewater are shown in Table 3.
  • Serial number project unit measured value Serial number project unit measured value 1 COD Cr Mg/L 9 5 Turbidity NTU 2 2 SS Mg/L 1 6 pH 7.2 3 Ammonia nitrogen Mg/L 0 7 total hardness Mg/L 350 4 Chroma 8 8 Conductivity ⁇ S/cm 1100
  • the papermaking advanced treated wastewater is extracted by the water supply pump 12 at a flow rate of 150 T/h, and then input into the nano catalytic electrolytic tank 13
  • the nano-catalyzed electrolyzed water directly enters the precipitation tank 14, neutralizes the precipitate, and removes solid impurities, plankton, bacteria, and colloids in the water to purify the wastewater through the ultrafiltration membrane system 22.
  • the papermaking advanced treatment wastewater has a lower salt content, firstly added industrial sodium chloride to adjust its salt content to 12.5 ⁇ , and then subjected to nano catalytic electrolysis, the working voltage of the nano catalytic electrolysis is 5-6 V, and the current density is 156-160 mA/cm 2 , nano-catalytic electrolysis produces nascent chlorine [Cl], hydroxyl and nascent oxygen [O] to kill microorganisms in wastewater, oxidize and decompose organic matter in wastewater, and make suspended matter in wastewater, After the colloid and charged particles form larger particles under the action of the electric field, the water is purified by the immersion ultrafiltration membrane filtration separation system, and the SDI is determined to be 1.9.
  • the purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation unit passes through the shutoff valve 41 and the water supply pump 42.
  • the concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
  • the electrodialysis system is a filled electrodialysis system (EDI), and the working conditions of electrodialysis are an operating voltage of 3.0 kg/cm 2 , an operating voltage of 150 to 250 V, and a current intensity of 2 to 3 A.
  • EDI electrodialysis system
  • the flow rates of the dialysate and concentrate were 118T/h and 32T/h, respectively, and the recovery rate of wastewater was 78.7%.
  • the quality of recycled water is shown in Table 5, and the indicators of concentrated wastewater are shown in Table 6.
  • Serial number project unit measured value Serial number project unit measured value 1 COD Cr Mg/L 30 5 Chroma 5 2 SS Mg/L 5 6 pH 7.7 3 Ammonia nitrogen Mg/L 0 7 hardness Mmmol/l 115 4 Turbidity NTU 2 8 Conductivity ⁇ S/cm 830
  • Serial number project unit measured value Serial number project unit measured value 1 COD Cr Mg/L 163 4 Salt content ⁇ 11.5 2 SS Mg/L 45 5 pH 8.2 3 Turbidity NTU 4.6 6 Conductivity ⁇ S/cm 9200
  • the papermaking advanced treatment wastewater is extracted by the water supply pump 12 at a flow rate of 250 T/h, and then input into the nano catalytic electrolysis machine 13
  • the nano-catalyzed electrolyzed water directly enters the precipitation tank 14, and after being precipitated, the ultra-filtration membrane system 22 removes solid impurities, plankton, bacteria, and colloids in the water to purify the wastewater.
  • the nano-catalytic electrolysis has an operating voltage of 5-6 V and a current intensity of 190-200 mA/cm 2 .
  • the nano-catalytic electrolysis produces nascent chlorine [Cl], hydroxyl and nascent oxygen [O] to kill microorganisms in the wastewater.
  • Oxidative decomposition of organic matter in the wastewater, and the suspension, colloid and charged particles in the wastewater form larger particles under the action of the electric field, and then the water purification wastewater is removed by the immersion ultrafiltration membrane filtration separation system, and the SDI is determined to be 1.7.
  • the purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation unit passes through the shutoff valve 41 and the water supply pump 42.
  • the concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
  • the electrodialysis system is a filled electrodialysis system (EDI), and the working conditions of electrodialysis are an operating voltage of 2.5 kg/cm 2 , an operating voltage of 180 to 250 V, and a current intensity of 2 to 3 A.
  • EDI electrodialysis system
  • the flow rates of the dialysate and concentrate are 200T/h and 50T/h, respectively, and the recovery rate of wastewater is 80.0%.
  • the quality of recycled water is shown in Table 8, and the indicators of concentrated wastewater are shown in Table 9.
  • Serial number project unit measured value Serial number project unit measured value 1 COD Cr Mg/L 32 5 Chroma 5 2 SS Mg/L not detected 6 pH 7.3 3 Ammonia nitrogen Mg/L 0.1 7 Conductivity ⁇ S/cm 900 4 Turbidity NTU 2 8 hardness Mmmol/l 230
  • the technical solution of the present invention is treated with wastewater, 70-85% It can be recycled and reused, which not only reduces wastewater discharge, avoids environmental pollution of wastewater, but also reduces water waste. It can also make the cost of recycled recycled water lower than the price of tap water, economically reasonable and produce better economic benefits. With good industrial applicability.

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  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

Provided is an electrochemistry and electrodialysis-based apparatus for recycling wastewater from papermaking. The recycling apparatus is provided with a nano-catalytic electrolysis system, a submerged ultrafiltration separation system, an ultrafiltration membrane cleaning system, and an electrodialysis system. Also provided is a method using the apparatus for recycling the wastewater from papermaking, comprising the following steps: extracting the wastewater from papermaking and introducing same into the nano-catalytic electrolysis system; flowing the wastewater from papermaking that is purified after processing into the submerged ultrafiltration separation system to acquire dialyzed water; then feeding the dialyzed water into the electrodialysis system for desalination by electrodialysis; and acquiring desalinated water and concentrated water.

Description

基于电化学和电渗析技术的造纸废水循环利用装置及方法  Papermaking wastewater recycling device and method based on electrochemical and electrodialysis technology 技术领域Technical field
本发明涉及一种造纸废水处理，特别是涉及一种基于电化学和电渗析技术的造纸废水循环利用装置及方法。  The invention relates to a papermaking wastewater treatment, in particular to a papermaking wastewater recycling device and method based on electrochemical and electrodialysis technology.
背景技术Background technique
制浆造纸废水是指化学法制浆产生的蒸煮废液（又称黑液、红液），洗浆漂白过程中产生的中段水及抄纸工序中产生的白水。一般每生产1t硫酸盐浆就有1t有机物和400kg碱类、硫化物溶解于黑液中；生产1t亚硫酸盐浆约有900kg有机物和200kg氧化物（钙、镁等）和硫化物溶于红液中。废液排入江河中不仅严重污染水源，而且会造成大量的资源浪费。造纸业是传统的用水大户，也是造成水污染的重要污染源之一。目前，我国造纸工业废水排放量及COD排放量均居我国各类工业排放量的首位，造纸工业对水环境的污染最为严重，它不但是我国造纸工业污染防治的首要问题，也是全国工业废水进行达标处理和节水的首要问题。据统计，我国县及县以上造纸及纸制品工业废水排放量占全国工业总排放量的18.6%，其中处理排放达标量占造纸工业废水总排放量的49.3%，排放废水中COD约占全国工业COD总排放量的44.0%。因此，如何消除造纸废水污染并使废液中的宝贵资源得到利用是一项具有重大社会意义和经济价值的工作，应当十分重视。随着经济的发展，我国日益面临淡水资源短缺、原料匮乏的问题，而另一方面，水污染也越来越严重。近年来，经多方不懈努力，造纸工业水污染防治已经取得了一定的成绩，虽然纸及纸板产量逐年增加，但排放废水中的COD却逐年降低。但是，目前造纸行业约占排放总量50%的废水尚未进行达标处理，造纸废水处理后再循环利用的更是少之又少，因此，造纸废水污染防治和循环使用任务还相当繁重。Pulp and papermaking wastewater refers to the cooking waste liquid (also known as black liquor, red liquor) produced by chemical pulping, the middle water produced during the washing and bleaching process, and the white water produced in the papermaking process. Generally, for every 1 t of kraft slurry, 1 t of organic matter and 400 kg of alkali and sulfide are dissolved in black liquor; 1 t of sulfite pulp is produced with about 900 kg of organic matter and 200 kg of oxide (calcium, magnesium, etc.) and sulfide are dissolved in red. In the liquid. The discharge of waste liquid into rivers not only seriously pollutes the water source, but also causes a large amount of waste of resources. The paper industry is a traditional water user and one of the important sources of water pollution. At present, China's paper industry wastewater discharge and COD emissions rank first in all types of industrial emissions in China. The paper industry has the most serious pollution to the water environment. It is not only the primary problem of pollution prevention and control in China's paper industry, but also the national industrial wastewater. The primary problem of compliance and water conservation. According to statistics, China's county and county paper and paper products industrial wastewater discharge accounted for 18.6% of the country's total industrial emissions, of which treatment discharge standards accounted for 49.3% of the total discharge of paper industry wastewater, COD emissions from wastewater accounted for national industry 44.0% of total COD emissions. Therefore, how to eliminate the pollution of papermaking wastewater and make use of valuable resources in waste liquid is a work of great social and economic value, which should be taken seriously. With the development of the economy, China is increasingly facing the shortage of fresh water resources and the shortage of raw materials. On the other hand, water pollution is becoming more and more serious. In recent years, through the unremitting efforts of many parties, the paper industry has achieved certain results in water pollution prevention and control. Although the output of paper and paperboard has increased year by year, the COD in wastewater discharge has been decreasing year by year. However, at present, the wastewater industry accounts for about 50% of the total discharge of wastewater, and the recycling of papermaking wastewater is rare. Therefore, the prevention and recycling of papermaking wastewater is quite arduous.
造纸废水成分复杂，可生化性差，属于较难处理的工业废水，其来源和特点是：Papermaking wastewater has complex composition and poor biodegradability. It is a difficult industrial wastewater. Its sources and characteristics are:
1．蒸煮工段废液1. Cooking section waste
即碱法制浆产生的黑液和酸法制浆产生的红液。我国绝大部分造纸厂采用碱法制浆而产生黑液。黑液中所含的污染物占到了造纸工业污染排放总量的90%以上，且具有高浓度和难降解的特性，它的治理一直是一大难题。黑液中的主要成分有3种，即木质素、聚戊糖和总碱。木质素是一类无毒的天然高分子物质，作为化工原料具有广泛的用途，聚戊糖可用作牲畜饲料。That is, the black liquor produced by alkaline pulping and the red liquor produced by acid pulping. Most paper mills in China use alkaline pulping to produce black liquor. The pollutants contained in the black liquor account for more than 90% of the total pollution discharge of the paper industry, and have high concentration and refractory characteristics. Its treatment has always been a major problem. There are three main components in the black liquor, namely lignin, polypentose and total alkali. Lignin is a kind of non-toxic natural high-molecular substance. It has a wide range of uses as a chemical raw material, and polypentose can be used as livestock feed.
2．中段水2. Middle water
制浆中段废水是指经黑液提取后的蒸煮浆料在筛选、洗涤、漂白等过程中排出的废水，颜色呈深黄色，占造纸工业污染排放总量的8%～9%，吨浆COD负荷310kg左右。中段水浓度高于生活污水，BOD和COD的比值在0.20到0.35之间，可生化性较差，有机物难以生物降解且处理难度大。中段水中的有机物主要是木质素、纤维素、有机酸等，以可溶性COD为主。其中，对环境污染最严重的是漂白过程中产生的含氯废水，例如氯化漂白废水、次氯酸盐漂白废水等。次氯酸盐漂白废水主要含三氯甲烷，还含有40多种其他有机氯化物，其中以各种氯代酚为最多，如二氯代酚、三氯代酚等。 此外，漂白废液中含有毒性极强的致癌物质二恶英，对生态环境和人体健康造成了严重威胁。The mid-stage pulping wastewater refers to the wastewater discharged from the cooking slurry after black liquor extraction in the process of screening, washing and bleaching. The color is dark yellow, accounting for 8% to 9% of the total pollution discharge of the paper industry. The load is about 310kg. The water concentration in the middle section is higher than that in domestic sewage. The ratio of BOD to COD is between 0.20 and 0.35. The biodegradability is poor, the organic matter is difficult to biodegrade and the treatment is difficult. The organic matter in the middle water is mainly lignin, cellulose, organic acid, etc., mainly soluble COD. Among them, the most serious environmental pollution is the chlorine-containing wastewater generated during the bleaching process, such as chlorinated bleaching wastewater and hypochlorite bleaching wastewater. Hypochlorite bleaching wastewater mainly contains chloroform and contains more than 40 kinds of other organic chlorides, among which various chlorophenols are the most, such as dichlorophenol and trichlorophenol. In addition, the bleaching waste liquid contains toxic dioxins, which are extremely toxic, posing a serious threat to the ecological environment and human health.
3．白水3. White water
白水即抄纸工段废水，它来源于造纸车间纸张抄造过程。白水主要含有细小纤维、填料、涂料和溶解了的木材成分，以及添加的胶料、湿强剂、防腐剂等，以不溶性COD为主，可生化性较低，其加入的防腐剂有一定的毒性。白水水量较大，但其所含的有机污染负荷远远低于蒸煮黑液和中段废水。现在几乎所有的造纸厂造纸车间都采用了部分或全封闭***以降低造纸耗水量，节约动力消耗，提高白水回用率，减少多余白水排放。White water is the papermaking section wastewater, which comes from the papermaking process in the papermaking workshop. White water mainly contains fine fibers, fillers, coatings and dissolved wood components, as well as added rubber compounds, wet strength agents, preservatives, etc., which are mainly insoluble COD, have low biodegradability, and have a certain preservative added. toxicity. White water has a large amount of water, but its organic pollution load is much lower than that of cooking black liquor and middle-stage wastewater. Almost all paper mill paper mills now use partial or fully enclosed systems to reduce paper consumption, save power, increase white water reuse, and reduce excess white water emissions.
目前，用于造纸废水处理的方法主要有：物理过滤法、混凝沉淀法、吸附法、高级氧化法、气浮法、加酸吸收法、催化氧化法、生化法等，每种方法都具有各种的优缺点。由于单一的处理方法很难达到效果，在实际运用中，通常是根据要处理废水的实际情况，将几种方法结合使用，典型的生产工艺是将造纸废水经过过滤等物理处理，然后经过絮凝沉淀后再经生化处理后达标排放。At present, the methods used for papermaking wastewater treatment mainly include: physical filtration method, coagulation sedimentation method, adsorption method, advanced oxidation method, air floatation method, acid absorption method, catalytic oxidation method, biochemical method, etc., each method has Various advantages and disadvantages. Since the single treatment method is difficult to achieve the effect, in practical application, several methods are usually combined according to the actual situation of the wastewater to be treated. The typical production process is to physically treat the papermaking wastewater through filtration and then flocculation and sedimentation. After the biochemical treatment, the standard is discharged.
有关造纸废水的处理已有一些报道，例如中国专利CN1125696公开一种造纸废水处理及循环使用方法，是在常温、常压条件下，采用物理—化学的方法，将蒸煮黑液及漂白废水经预处理分离草浆——酸化分离——中和 ——酸碱分离脱色的处理过程，废水中的草浆、木质素、烧碱全部回收利用，处理后的水供蒸煮、漂白使用，在处理过程中，不产生二次污染，采用计算机测控的静态混合器，占地面积小，投资少，运行费用低，效率高，安装使用方便，适用于亚铵法之外的草类制浆企业。中国专利CN101205107公开一种对造纸废水处理并循环利用的方法，主要包括湿浆回收、混凝沉淀、三相厌氧处理、脱硫、生物铁法处理、过滤消毒和循环回用等步骤。该发明先对造纸废水进行预处理，再对预处理过的出水进行生物铁法处理，使活性污泥形成结构紧密、颗粒细小、比表面积大、脱水性好的团粒状铁污泥，再利用A/O活性污泥处理***进行生化作用，对生产高档纸的用水还采用微絮凝过滤技术进行深度处理，使出水水质更好。 There have been some reports on the treatment of papermaking wastewater. For example, Chinese patent CN1125696 discloses a method for treating and recycling papermaking wastewater, which is a physical-chemical method for preheating black liquor and bleaching wastewater under normal temperature and normal pressure conditions. Treatment of separated straw pulp - acidification separation - neutralization ——The treatment process of acid-base separation and decolorization, the straw pulp, lignin and caustic soda in the wastewater are all recycled, and the treated water is used for cooking and bleaching. In the process of treatment, no secondary pollution occurs, and static measurement by computer is used. The mixer has a small footprint, low investment, low operating cost, high efficiency, convenient installation and use, and is suitable for grass pulping enterprises other than the ammonium imide method. Chinese patent CN101205107 discloses a method for treating and recycling papermaking wastewater, which mainly comprises steps of wet pulp recovery, coagulation sedimentation, three-phase anaerobic treatment, desulfurization, bio-iron treatment, filtration sterilization and recycling. The invention firstly pretreats the papermaking wastewater, and then carries out the bio-iron treatment on the pre-treated effluent, so that the activated sludge forms a granular iron sludge with compact structure, small particle size, large specific surface area and good dehydration, and reused. The A/O activated sludge treatment system carries out biochemical action, and the water for producing high-grade paper is further treated by micro-flocculation filtration technology to make the effluent water quality better.
技术问题technical problem
本发明的目的在于针对现有的造纸废水处理方法所存在的成本较高、效能较低、处理后的废水多为排放、没有深度处理循环利用、浪费水资源等问题，提供一种成本较低、效能较高、可循环利用的基于电化学和电渗析技术的造纸废水循环利用装置及方法。 The object of the present invention is to provide a lower cost for the existing papermaking wastewater treatment method, such as high cost, low efficiency, mostly treated wastewater, no deep treatment recycling, waste of water resources and the like. A papermaking wastewater recycling device and method based on electrochemical and electrodialysis technology with high efficiency and recyclability.
本发明所述造纸废水是经过传统的过滤、絮凝和生化处理后二沉池达到排放三级以上排放标准的造纸废水。 The papermaking wastewater of the invention is a papermaking wastewater which has reached the discharge standard of discharge level III by the secondary settling tank after the conventional filtration, flocculation and biochemical treatment.
技术解决方案Technical solution
本发明所述基于电化学和电渗析技术的造纸废水循环利用装置设有： The papermaking wastewater recycling device based on electrochemical and electrodialysis technology of the invention has:
纳米催化电解***，纳米催化电解***设有截止阀、水泵、纳米催化电解机、缓冲沉淀罐和过滤机；截止阀的进口外接造纸废水二沉池排放口，水泵的进口接截止阀的出口，水泵的出口接纳米催化电解机的进口，纳米催化电解机的出口与缓冲沉淀罐的进口联接，缓冲沉淀罐的出口经过水泵与过滤机的进口联接；The nano catalytic electrolysis system has a shut-off valve, a water pump, a nano catalytic electrolysis machine, a buffer sedimentation tank and a filter; the inlet of the shut-off valve is externally connected to the discharge port of the second sedimentation tank of the papermaking wastewater, and the inlet of the water pump is connected to the outlet of the shut-off valve. The outlet of the water pump is connected to the inlet of the nano catalytic electrolysis machine, the outlet of the nano catalytic electrolysis machine is connected with the inlet of the buffer sedimentation tank, and the outlet of the buffer sedimentation tank is connected through the inlet of the water pump and the filter;
浸没式超滤膜过滤分离***：浸没式超滤膜过滤分离***用于将纳米催化电解***所得的净化废水过滤、分离得透析水和浓缩水，浸没式超滤膜过滤分离***设有截止阀、浸没式超滤膜池、鼓风机、曝气器、超滤膜***、抽吸泵和透析水贮罐，所述截止阀的进口经进水管与纳米催化电解***的过滤机出口连接，截止阀出口接浸没式超滤膜池，超滤膜浸没在浸没式超滤膜池中的印染净化废水中，抽吸泵从超滤膜内侧将水负压抽吸过膜壁，产生的透析水通过抽吸泵收集到透析水贮罐用于进一步经过电渗析脱盐得供生产上循环利用的再生水。截止阀的进口接纳米催化电解***沉淀罐的出口，截止阀的出口接浸没式超滤膜池的进口，浸没式超滤膜池的出口依次经过抽吸泵、截止阀进入透析水贮罐；Immersion ultrafiltration membrane filtration separation system: immersion ultrafiltration membrane filtration separation system is used to filter and separate the purified wastewater obtained by the nano catalytic electrolysis system into dialysis water and concentrated water. The immersion ultrafiltration membrane filtration separation system is provided with a shut-off valve. , immersion ultrafiltration membrane tank, blower, aerator, ultrafiltration membrane system, suction pump and dialysis water storage tank, the inlet of the shut-off valve is connected with the filter outlet of the nano catalytic electrolysis system through the inlet pipe, the shut-off valve The outlet is connected to the immersion ultrafiltration membrane tank, and the ultrafiltration membrane is immersed in the printing and dyeing purification wastewater in the immersion ultrafiltration membrane tank, and the suction pump sucks the water negative pressure from the inner side of the ultrafiltration membrane through the membrane wall, and the generated dialysis water passes. The suction pump collects the dialysis water storage tank for further desalination by electrodialysis to obtain recycled water for recycling in production. The inlet of the shut-off valve is connected to the outlet of the precipitation tank of the nano catalytic electrolysis system, the outlet of the shut-off valve is connected to the inlet of the immersion ultrafiltration membrane tank, and the outlet of the immersion ultrafiltration membrane tank is sequentially passed through the suction pump and the shut-off valve into the dialysis water storage tank;
超滤膜清洗***：超滤膜清洗***用于清洗超滤膜过滤分离***，超滤膜清洗***设有清洗液罐、反冲洗泵、截止阀和联接管道，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，截止阀的出口接超滤膜***；Ultrafiltration membrane cleaning system: The ultrafiltration membrane cleaning system is used to clean the ultrafiltration membrane filtration separation system. The ultrafiltration membrane cleaning system is provided with a cleaning liquid tank, a backwashing pump, a shut-off valve and a connecting pipe, and the outlet of the cleaning liquid tank is backwashed. The inlet of the pump, the outlet of the backwashing pump is connected to the inlet of the shut-off valve, and the outlet of the shut-off valve is connected to the ultrafiltration membrane system;
电渗析***：电渗析***设有截止阀、供水泵、电渗析机、透析水贮罐和浓缩水贮罐；截止阀的进口接浸没式超滤膜过滤分离***透析水贮罐的出口，截止阀的出口接供水泵的进口，供水泵的出口接电渗析机的进口，电渗析机的透析水出口接透析水贮罐，电渗析的浓缩水出口接浓缩水贮罐。Electrodialysis system: electrodialysis system is equipped with a shut-off valve, water supply pump, electrodialysis machine, dialysis water storage tank and concentrated water storage tank; the inlet of the shut-off valve is connected to the outlet of the dialysis water storage tank of the immersion ultrafiltration membrane filtration separation system. The outlet of the valve is connected to the inlet of the water supply pump, the outlet of the water supply pump is connected to the inlet of the dialysis machine, the dialysis water outlet of the electrodialysis machine is connected to the dialysis water storage tank, and the concentrated water outlet of the electrodialysis is connected to the concentrated water storage tank.
所述浸没式超滤膜过滤***可去除废水中的固体杂质、浮游生物、细菌、胶体等，浸没式膜采用外压开放式过滤设计，可被直接浸入到废水中，因此***的占地面积小。其工作条件是：常温～45℃，工作压力为3～50kPa。The immersed ultrafiltration membrane filtration system can remove solid impurities, plankton, bacteria, colloids and the like in the waste water, and the immersion membrane adopts an external pressure open filtration design, and can be directly immersed in the waste water, so the system covers the area. small. The working conditions are: normal temperature ~ 45 ° C, working pressure is 3 ~ 50 kPa.
所述电渗析***可选用倒极电渗析***（EDR）、液膜电渗析***（EDLM）、填充电渗析***（EDI）、双极性电渗析***（EDMB）或无极水电渗析***等。The electrodialysis system may be selected from an inverted electrodialysis system (EDR), a liquid membrane electrodialysis system (EDLM), a filled electrodialysis system (EDI), a bipolar electrodialysis system (EDMB) or a stepless hydroelectric dialysis system.
所述电渗析***可以将经过浸没式超滤膜过滤分离***所得透析水经过电渗析分离成透析水（脱盐水）和浓缩水，使其满足工业生产中不同的生产工艺用水的质量要求。电渗析的工作条件为0.5～3.0kg/cm2，操作电压为50～250V，电流强度为1～3A。The electrodialysis system can separate the dialysis water obtained by the immersion ultrafiltration membrane filtration separation system into dialysis water (desalted water) and concentrated water by electrodialysis to meet the quality requirements of different production process waters in industrial production. The working conditions for electrodialysis are 0.5 to 3.0 kg/cm 2 , the operating voltage is 50 to 250 V, and the current intensity is 1 to 3 A.
所述电渗析***可以根据废水中的含盐量进行一段脱盐、两段脱盐或三段脱盐，从而使再生水的含盐量满足工业生产的工艺用水要求，其脱盐率可以达45～80%。The electrodialysis system can perform one-stage desalting, two-stage desalting or three-stage desalting according to the salt content in the wastewater, so that the salt content of the reclaimed water meets the process water requirement of industrial production, and the salt rejection rate can reach 45-80%.
本发明所述基于电化学和电渗析技术的造纸废水循环利用方法包括以下步骤：The papermaking wastewater recycling method based on electrochemical and electrodialysis technology of the present invention comprises the following steps:
1）纳米催化电解：将造纸废水经水泵提取后，输入纳米催化电解机中进行催化微电解后，输入多介质过滤机进行过滤，除去废水中因固体杂质、浮游生物、细菌、胶体得净化废水，测定其SDI应小于5；1) Nano-catalytic electrolysis: After the papermaking wastewater is extracted by water pump, it is input into the nano-catalytic electrolysis machine for catalytic micro-electrolysis, and then input into a multi-media filter for filtration to remove waste water from the wastewater due to solid impurities, plankton, bacteria and colloids. , determine that its SDI should be less than 5;
在步骤1）中，所述造纸废水的氯化钠含量可为6‰～30‰，最好为0.6‰～1.3‰，氯化钠含量不够时可添加工业氯化钠补充至6‰～50‰；所述纳米催化电解的工作电压可为2～500V，两个极板间的电压差为2～18V ，最佳电压差为4～10V，电流密度可为5～300 mA/cm2，最佳电流密度为50～200 mA/cm2，造纸深度处理废水经过电解产生初生态的强氧化性物质氧化分解氧化分解废水中的有机物，脱除色度，絮凝沉降杂质、降低COD和杀灭微生物；所述纳米催化电解是将造纸深度处理废水经过纳米催化，废水在电解罐中的停留时间2～４min，电解使之生成初生态的强氧化性物质，用以氧化分解废水中的有机物，杀灭废水中微生物，同时，在电场作用下使废水中的悬浮物、胶体、带电微粒凝聚形成较大颗粒；所述过滤为砂滤或多介质过滤或微滤的一种。将催化电解所得废水经过砂滤、多介质过滤或微滤，其所得废水的色度为1～6，COD为50～300mg/L，氨氮为0～10mg/L，SS为0～10mg/L。所述造纸深度处理废水是指造纸废水经过现有的造纸废水处理方法和设施进行处理，达到三级以上排放标准的处理后废水。In the step 1), the sodium chloride content of the papermaking wastewater may be 6 ‰ 30 ‰, preferably 0.6 ‰ to 1.3 ‰, and the sodium chloride content may be insufficient to add industrial sodium chloride to 6 ‰ 50 The working voltage of the nano catalytic electrolysis can be 2 to 500 V, the voltage difference between the two plates is 2 to 18 V, the optimum voltage difference is 4 to 10 V, and the current density can be 5 to 300 mA/cm 2 . The optimum current density is 50-200 mA/cm 2 , and the papermaking advanced treatment wastewater is electrolyzed to produce eutectic strong oxidizing substances, oxidative decomposition, oxidative decomposition of organic matter in wastewater, removal of color, flocculation and sedimentation of impurities, reduction of COD and killing Microbial; the nano-catalytic electrolysis is to subject the papermaking advanced treatment wastewater to nano-catalysis, and the residence time of the wastewater in the electrolysis tank is 2 to 4 minutes, and electrolysis is used to generate an initial ecological strong oxidizing substance for oxidative decomposition of organic matter in the wastewater. The microorganisms in the wastewater are killed, and at the same time, suspended matter, colloids and charged particles in the wastewater are agglomerated to form larger particles under the action of an electric field; the filtration is one of sand filtration or multi-media filtration or microfiltration. The wastewater obtained by catalytic electrolysis is subjected to sand filtration, multi-media filtration or microfiltration, and the obtained wastewater has a chromaticity of 1 to 6, a COD of 50 to 300 mg/L, an ammonia nitrogen of 0 to 10 mg/L, and an SS of 0 to 10 mg/L. . The papermaking advanced treatment wastewater refers to the treated wastewater after the papermaking wastewater is treated by the existing papermaking wastewater treatment method and facilities to reach the discharge standard of the third grade or above.
2）浸没式超滤过滤：将经过纳米催化电解***系处理后的净化印染废水经管道流入浸没式超滤***过滤处理，得透析水；2) immersion ultrafiltration filtration: the purified printing and dyeing wastewater treated by the nano catalytic electrolysis system is filtered into a submerged ultrafiltration system through a pipeline to obtain dialysis water;
在步骤2）中，所述超滤***过滤处理的工作条件可为：常温～45℃，工作压力可为3～50kPa；所得透析水的的色度为1～3，COD为20～100mg/L，氨氮为0～1mg/L，SS为0～1mg/L。In the step 2), the working condition of the ultrafiltration system filtration treatment may be: normal temperature to 45 ° C, working pressure may be 3 to 50 kPa; the obtained dialysis water has a chromaticity of 1 to 3, and the COD is 20 to 100 mg / L, ammonia nitrogen is 0 to 1 mg/L, and SS is 0 to 1 mg/L.
3）电渗析：将经过步骤2）的浸没式超滤过滤处理所得的透析水经过水泵送入电渗析***，进行电渗析脱盐，得脱盐水和浓缩水。其所得脱盐水的的色度为1～2，COD为10～50mg/L，氨氮不得检出，SS不得检出，总硬度小于350mg/L。3) Electrodialysis: The dialysis water obtained by the immersion ultrafiltration filtration treatment of the step 2) is sent to an electrodialysis system by water pumping, and electrolyzed and desalted to obtain desalted water and concentrated water. The color of the obtained desalinated water is 1-2, the COD is 10-50 mg/L, the ammonia nitrogen is not detected, the SS is not detected, and the total hardness is less than 350 mg/L.
在步骤3）中，所述电渗析***的工作条件可为0.5～3.0kg/cm2，操作电压可为50～250V，电流强度可为1～3A。In step 3), the electrodialysis system may have an operating condition of 0.5 to 3.0 kg/cm2, an operating voltage of 50 to 250 V, and a current intensity of 1 to 3 A.
有益效果Beneficial effect
本发明既克服了单用膜过滤分离处理，又克服了常规的造纸废水方法的废水处理效果不理想，排放的废水污染环境的缺陷，并且可以化腐朽为神气，变废物为资源，将现有的造纸深度处理废水净化及回收循环利用。与现有技术比较，具有以下突出优点：The invention not only overcomes the single-use membrane filtration separation treatment, but also overcomes the unsatisfactory wastewater treatment effect of the conventional papermaking wastewater method, and the waste water pollutes the environment, and can turn the decay into the spirit, change the waste into the resource, and the existing The papermaking process treats wastewater purification and recycling. Compared with the prior art, it has the following outstanding advantages:
（1） 大量减少絮凝剂量的用量，减少单位产品化学药剂的消耗和节约药剂成本；(1) Reducing the amount of flocculating dose in a large amount, reducing the consumption of chemical agents per unit product and saving the cost of pharmaceuticals;
（2） 大量减少污泥的排放量，减少污泥处理成本；(2) Significantly reduce sludge discharge and reduce sludge treatment costs;
（3） 废水经过处理，70～85%可以再生循环利用，既减少废水排放，避免废水对环境污染，又减少水资源浪费，还可以使再生的循环水成本低于自来水价格，经济合理，产生较好的经济效益。(3) After the wastewater is treated, 70-85% can be recycled and reused, which not only reduces wastewater discharge, avoids environmental pollution of wastewater, but also reduces water waste. It can also make the cost of recycled circulating water lower than the price of tap water, economically reasonable, and produce better. Economic benefits.
（4）生化后造纸废水经过纳米催化电解，进一步降低COD，一是可以使废水的回用率提高，既减少废水排放，避免废水对环境污染，又减少水资源浪费，二是能杀灭废水中的细菌等微生物，根除膜的生物污染，大幅度减少膜的清洗次数，降低膜清洁再生成本，提高膜的使用效率，延长膜的使用寿命，减少膜更换成本；(4) Biochemical post-papermaking wastewater undergoes nano-catalytic electrolysis to further reduce COD. First, it can improve the reuse rate of wastewater, reduce wastewater discharge, avoid wastewater pollution to the environment, and reduce water waste. Second, it can kill wastewater. The microorganisms such as bacteria remove the bio-contamination of the membrane, greatly reduce the number of membrane cleanings, reduce the cost of membrane cleaning and regeneration, increase the efficiency of membrane use, prolong the service life of the membrane, and reduce the cost of membrane replacement;
（5）大幅度降低造纸废水COD的总排放量，使深度处理后废水的水COD的总排放量与二沉池直接排放比较下降25～40%；(5) Significantly reduce the total COD emission of papermaking wastewater, so that the total COD emission of wastewater after deep treatment is reduced by 25-40% compared with the direct discharge of the secondary sedimentation tank;
（6）大幅度降低吨纸的水消耗指标和废水排放指标，提高企业经济技术指标；(6) Substantially reduce water consumption indicators and wastewater discharge indicators of tons of paper, and improve economic and technical indicators of enterprises;
（7）采用电渗析技术部分脱盐替代反渗透脱盐，既可以使脱盐水满足造纸工艺用水的技术要求，又可以减少用电量，节省能源和降低成本；(7) Partial desalination instead of reverse osmosis desalination by electrodialysis technology can not only make desalted water meet the technical requirements of papermaking process water, but also reduce electricity consumption, save energy and reduce cost;
（8）采用电渗析技术脱盐替代反渗透脱盐，既可以减少固定资产投资，又可以提高废水利用率。(8) The use of electrodialysis technology for desalination instead of reverse osmosis desalination can not only reduce investment in fixed assets, but also improve wastewater utilization.
（9）采用纳米催化电解具有如下突出效果：(9) The use of nano-catalytic electrolysis has the following outstanding effects:
1）用纳米催化电解产生的初生态的强氧化性物质杀灭废水中微生物，使废水中微生物活体下降到30个/ml以下，消除微生物对膜材料的污染。1) The pre-ecologically strong oxidizing substances produced by nano-catalytic electrolysis kill the microorganisms in the wastewater, so that the microbial living organisms in the wastewater are reduced to less than 30/ml, and the microbial contamination of the membrane material is eliminated.
2）氧化分解废水中的有机物，残留染料快速分解脱色和降低CODCr。2) Oxidative decomposition of organic matter in wastewater, residual dyes rapidly decompose and decolorize and reduce COD Cr .
3）使废水中的悬浮物、胶体、带电微粒在电场作用下凝聚形成较大颗粒后，经过多介质过滤去除使水废水净化。3) After the suspended solids, colloids and charged particles in the wastewater are condensed under the action of an electric field to form larger particles, the water is purified by multi-media filtration.
4）废水中的重金属离子向电解罐的阴极移动，在阴极形成沉淀，从而降低废水中的重金属离子含量。4) Heavy metal ions in the wastewater move toward the cathode of the electrolytic tank to form a precipitate at the cathode, thereby reducing the content of heavy metal ions in the wastewater.
（10）经过了生化、化学、物化等多种方法处理后的深度处理废水的还有较深的颜色和较高的CODCr，一般的化学处理方法很难进一步脱色和降低COD Cr ，在自然环境下，很难退色。采用纳米催化电解对深度处理废水进行处理，能在2～5min内，使废水脱色和大幅度降低CODCr。(10) Deep treatment of wastewater after biochemical, chemical, physicochemical and other methods has deeper color and higher COD.Cr, general chemical treatment methods are difficult to further decolorize and reduce COD Cr In the natural environment, it is difficult to fade. The treatment of advanced treatment wastewater by nano-catalytic electrolysis can decolorize wastewater and greatly reduce COD within 2 to 5 minutes.Cr.
附图说明DRAWINGS
图 1 为本发明所述基于电化学和电渗析技术的造纸废水循环利用装置实施例的结构组成示意图。  1 is a schematic structural view of an embodiment of a papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to the present invention.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
本发明是在对现有深度处理造纸废水的成份、性质和现有处理方案进行深入***的对比研究之后完成的对深度处理后造纸废水的净化和再生循环利用工艺的设计，它通过纳米催化电解、过滤、浸没式超过滤、电渗析脱盐等方法的组合运用，从而形成一种特别适合于深度处理造纸废水的净化及再生循环利用方法。 The invention is a design of a process for purifying and recycling a papermaking wastewater after deep treatment after an in-depth systematic comparative study on the composition, properties and existing treatment schemes of the existing advanced treatment papermaking wastewater, which adopts nano catalytic electrolysis The combination of filtration, immersion ultrafiltration, electrodialysis desalination, etc., to form a purification and regeneration recycling method that is particularly suitable for the advanced treatment of papermaking wastewater.
下面实施例将结合附图对本发明作进一步的说明。 The invention will be further illustrated by the following examples in conjunction with the drawings.
参见图 1 ，本发明所述基于电化学和电渗析技术的造纸废水循环利用装置实施例设有： Referring to FIG. 1 , an embodiment of a papermaking wastewater recycling device based on electrochemical and electrodialysis technology of the present invention is provided with:
纳米催化电解***：纳米催化电解***用于纳米催化电解、沉淀等处理步骤。纳米催化电解***设有截止阀 11 、供水泵 12 、纳米催化电解机 13 、沉淀罐 14 ；截止阀 11 的进口外接印染废水（二沉池）排出口，供水泵 12 的进口接截止阀 11 的出口，供水泵 12 的出口接纳米催化电解机 13 的进口，纳米催化电解罐 13 的出口接沉淀罐 14 的进口。 Nano Catalytic Electrolysis System: Nano Catalytic Electrolysis System is used for nano catalytic electrolysis, precipitation and other processing steps. Nano catalytic electrolysis system with shut-off valve 11 Water supply pump 12 , nano catalytic electrolysis machine 13 , sedimentation tank 14 ; the inlet of the shut-off valve 11 is connected to the discharge port of the printing and dyeing wastewater (second settling tank), the inlet of the water supply pump 12 is connected to the outlet of the shut-off valve 11 , the water supply pump The outlet of 12 is connected to the inlet of the nano catalytic electrolysis machine 13, and the outlet of the nano catalytic electrolytic tank 13 is connected to the inlet of the precipitation tank 14.
浸没式超滤膜过滤分离***：浸没式超滤膜过滤分离***用于将纳米催化电解***所得印染净化废水过滤、分离得透析液（水）和浓缩液（水）。浸没式超滤膜过滤分离***设有截止阀 21 、超滤膜*** 22 、鼓风机 23 、曝气器 24 、浸没式超滤膜池 25 、抽吸泵 26 、截止阀 27 和透析液（水）贮罐 28 ；截止阀 21 的进口接纳米催化电解***沉淀罐 14 的出口，截止阀 21 的出口接浸没式超滤膜池 25 的进口，浸没式超滤膜池 25 的出口依次经过水泵 26 、截止阀 27 进入透析液（水）贮罐 28 。 Immersion ultrafiltration membrane filtration separation system: The immersion ultrafiltration membrane filtration separation system is used for filtering and separating the printing and dyeing wastewater obtained by the nano catalytic electrolysis system to obtain dialysate (water) and concentrate (water). Immersion ultrafiltration membrane filtration separation system with shut-off valve 21, ultrafiltration membrane system 22, blower 23, aerator 24, submerged ultrafiltration membrane tank 25, suction pump 26, shut-off valve 27 and dialysate (water) storage tank 28; shut-off valve 21 The inlet is connected to the outlet of the precipitation tank 14 of the nano catalytic electrolysis system, the outlet of the shut-off valve 21 is connected to the inlet of the submerged ultrafiltration membrane tank 25, and the outlet of the submerged ultrafiltration membrane tank 25 is sequentially passed through the water pump 26 and the shut-off valve. 27 Enter the dialysate (water) tank 28 .
超滤膜清洗***：超滤膜清洗***用于清洗超滤膜过滤分离***，设有清洗液罐 31 、反冲洗泵 32 、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 的出口接超滤膜*** 22 。 Ultrafiltration membrane cleaning system: Ultrafiltration membrane cleaning system for cleaning ultrafiltration membrane filtration separation system, with cleaning fluid tank 31, backwash pump 32 , shut-off valve 33. The outlet of the cleaning fluid 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, and the outlet of the shut-off valve 33 is connected to the ultrafiltration membrane system 22 .
电渗析***：电渗析***设有截止阀41、供水泵42、电渗析机43、透析液（水）贮罐44、浓缩液（水）贮罐45。浸没式超滤***所得印染净化废水通过截止阀41、供水泵42进入电渗析机43，电渗析机43的透析液（水）出口接透析液（水）贮罐44，电渗析机43的浓缩液（水）出口接浓缩液（水）贮罐45。 Electrodialysis system: The electrodialysis system is provided with a shut-off valve 41, a water supply pump 42, an electrodialysis machine 43, a dialysate (water) storage tank 44, and a concentrate (water) storage tank 45. The printing and dyeing wastewater obtained by the immersion ultrafiltration system enters the electrodialysis machine 43 through the shut-off valve 41 and the water supply pump 42, and the dialysate (water) outlet of the electrodialysis machine 43 is connected to the dialysate (water) storage tank 44, and the electrodialyzer 43 is concentrated. The liquid (water) outlet is connected to a concentrate (water) storage tank 45.
本发明的实施方式Embodiments of the invention
以下给出采用图 1 所示的所述基于电化学和电渗析技术的造纸废水循环利用装置实施的造纸废水的净化再生循环利用方法。 The following shows the use of Figure 1 The method for purifying and recycling the papermaking wastewater implemented by the papermaking wastewater recycling device based on the electrochemical and electrodialysis technology is shown.
实施例 1 Example 1
150 吨/日造纸深度处理废水的净化再生循环利用方法。 Purification and recycling of 150 tons/day papermaking wastewater.
所述造纸深度处理废水经测定指标如表 1 所示。 The measured indexes of the papermaking advanced treated wastewater are shown in Table 1.
表 1
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 186 4 色度 80
2 SS mg/L 90 5 pH 7.5
3 浊度 NTU 6 6 电导率 µS/cm 3200
Table 1
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 186 4 Chroma 80
2 SS Mg/L 90 5 pH 7.5
3 Turbidity NTU 6 6 Conductivity μS/cm 3200
150吨印染深度处理废水经供水泵12按7.5T/h 的流速提取后，输入纳米催化电解机13 中，纳米催化电解水直接进入沉淀罐 14 ，沉淀后进入浸没超滤膜***除去水中的固体杂质、浮游生物、细菌、胶体得净化废水。 150 tons of printing and dyeing advanced treatment wastewater is extracted by the water supply pump 12 at a flow rate of 7.5 T/h, and then input into the nano catalytic electrolysis machine 13 In the middle, the nano-catalyzed electrolyzed water directly enters the precipitation tank 14 , and after sedimentation, it enters the immersion ultrafiltration membrane system to remove solid impurities, plankton, bacteria and colloids in the water to purify the wastewater.
所述纳米催化电解的工作电压为8～9V ，电流密度为50 mA/cm2 ，纳米催化电解产生的初生态的氯 [Cl] 、羟基和初生态氧 [O] ，杀灭废水中微生物、氧化分解废水中的有机物，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后，经过浸没式超滤膜过滤分离***去除，使废水净化，测定 SDI 为1.9 。The nano catalytic electrolysis has an operating voltage of 8 to 9 V and a current density of 50 mA/cm 2 , and the nascent chlorine [Cl], hydroxyl group and nascent oxygen [O] produced by nano catalytic electrolysis kills microorganisms in the wastewater, The organic matter in the wastewater is oxidatively decomposed, and the suspended solids, colloids and charged particles in the wastewater are formed into larger particles under the action of an electric field, and then removed by an immersed ultrafiltration membrane filtration separation system to purify the wastewater, and the SDI is determined to be 1.9.
经过纳米催化电解单元和浸没式超滤膜过滤分离***净化所得的净化废水经过截止阀 41 、供水泵 42 进入电渗析机 43 中进行电渗析脱盐处理，分离成透析液（水）和浓缩液，透析液（水）经过透析液（水）出口和管道进入透析液（水）贮罐 44 ，浓缩液经过浓缩水出口和管道进入浓缩水贮罐 45 中。 The purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation system passes through the shut-off valve 41 and the water supply pump 42 Entering the electrodialysis machine 43 for electrodialysis desalination, separating into dialysate (water) and concentrate, dialysate (water) passing through the dialysate (water) outlet and piping into the dialysate (water) storage tank 44 The concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
所述电渗析***为倒极电渗析***（EDR ） ， 电渗析的工作条件是操作电压0.5 ㎏/㎝2 ，操作电压50～250V ，电流强度1～3A 。The electrodialysis system is an inverted electrodialysis system (EDR), and the working conditions of electrodialysis are an operating voltage of 0.5 kg/cm 2 , an operating voltage of 50 to 250 V, and a current intensity of 1 to 3 A.
所述透析液和浓缩液的流速分别为6.5T/h 和1.0T/h ，废水的回收率为86.7% ，回用水的质量如表 2 所示，浓缩废水的指标如表 3 所示。 The flow rates of the dialysate and concentrate are 6.5T/h and 1.0T/h, respectively, and the recovery rate of wastewater is 86.7%. The quality of recycled water is shown in Table 2, and the indicators of concentrated wastewater are shown in Table 3.
表 2
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 9 5 浊度 NTU 2
2 SS mg/L 1 6 pH 7.2
3 氨氮 mg/L 0 7 总硬度 mg/L 350
4 色度 8 8 电导率 µS/cm 1100
Table 2
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 9 5 Turbidity NTU 2
2 SS Mg/L 1 6 pH 7.2
3 Ammonia nitrogen Mg/L 0 7 total hardness Mg/L 350
4 Chroma 8 8 Conductivity μS/cm 1100
表 3
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 133 4 色度 40
2 SS mg/L 60 5 pH 7.9
3 浊度 NTU 9 6 电导率 µS/cm 7600
table 3
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 133 4 Chroma 40
2 SS Mg/L 60 5 pH 7.9
3 Turbidity NTU 9 6 Conductivity μS/cm 7600
实施例 2 Example 2
3000吨/日造纸深度处理废水的净化及循环利用方法。 Purification and recycling method of 3000 tons/day papermaking advanced treatment wastewater.
所述造纸深度处理废水经测定，指标如表 4 所示： The papermaking advanced treatment wastewater was measured, and the indicators are shown in Table 4:
表 4
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 109 4 色度 120
2 SS mg/L 75 5 pH 7.5
3 浊度 NTU 6 6 电导率 µS/cm 2300
Table 4
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 109 4 Chroma 120
2 SS Mg/L 75 5 pH 7.5
3 Turbidity NTU 6 6 Conductivity μS/cm 2300
造纸深度处理废水经供水泵12按150T/h 流速提取后，输入纳米催化电解罐13 中，纳米催化电解水直接进入沉淀罐14 ，中和沉淀后经超滤膜***22 除去水中的固体杂质、浮游生物、细菌、胶体得净化废水。 The papermaking advanced treated wastewater is extracted by the water supply pump 12 at a flow rate of 150 T/h, and then input into the nano catalytic electrolytic tank 13 The nano-catalyzed electrolyzed water directly enters the precipitation tank 14, neutralizes the precipitate, and removes solid impurities, plankton, bacteria, and colloids in the water to purify the wastewater through the ultrafiltration membrane system 22.
所述造纸深度处理废水由于含盐量较低，先加入工业氯化钠将其含盐量调节到12.5‰ ，然后再进行纳米催化电解，纳米催化电解的工作电压为5～6V ，电流密度为156～160mA/cm2 ，纳米催化电解产生初生态的氯 [Cl] 、羟基和初生态氧 [O] ，以杀灭废水中微生物、氧化分解废水中的有机物，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后，经过浸没式超滤膜过滤分离***去除使水净化废水，测定SDI 为1.9 。The papermaking advanced treatment wastewater has a lower salt content, firstly added industrial sodium chloride to adjust its salt content to 12.5 ‰, and then subjected to nano catalytic electrolysis, the working voltage of the nano catalytic electrolysis is 5-6 V, and the current density is 156-160 mA/cm 2 , nano-catalytic electrolysis produces nascent chlorine [Cl], hydroxyl and nascent oxygen [O] to kill microorganisms in wastewater, oxidize and decompose organic matter in wastewater, and make suspended matter in wastewater, After the colloid and charged particles form larger particles under the action of the electric field, the water is purified by the immersion ultrafiltration membrane filtration separation system, and the SDI is determined to be 1.9.
经过纳米催化电解单元和浸没式超滤膜过滤分离单元净化所得的净化废水经过经过截止阀 41 、供水泵 42 进入电渗析机 43 中进行电渗析脱盐处理，分离成透析液（水）和浓缩液，透析液（水）经过透析液（水）出口和管道进入透析液（水）贮罐 44 ，浓缩液经过浓缩水出口和管道进入浓缩水贮罐 45 中。 The purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation unit passes through the shutoff valve 41 and the water supply pump 42. Entering the electrodialysis machine 43 for electrodialysis desalination, separating into dialysate (water) and concentrate, dialysate (water) passing through the dialysate (water) outlet and piping into the dialysate (water) storage tank 44 The concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
所述电渗析***为填充电渗析***（ EDI ） ， 电渗析的工作条件是操作电压3.0 ㎏/㎝2 ，操作电压150～250V ，电流强度2～3A 。The electrodialysis system is a filled electrodialysis system (EDI), and the working conditions of electrodialysis are an operating voltage of 3.0 kg/cm 2 , an operating voltage of 150 to 250 V, and a current intensity of 2 to 3 A.
所述透析液和浓缩液的流速分别为118T/h 和32T/h ，废水的回收率为78.7% ，回用水的质量如表 5 所示，浓缩废水的指标如表6 所示。 The flow rates of the dialysate and concentrate were 118T/h and 32T/h, respectively, and the recovery rate of wastewater was 78.7%. The quality of recycled water is shown in Table 5, and the indicators of concentrated wastewater are shown in Table 6.
表 5
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 30 5 色度 5
2 SS mg/L 5 6 pH 7.7
3 氨氮 mg/L 0 7 硬度 mmol/l 115
4 浊度 NTU 2 8 电导率 µS/cm 830
table 5
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 30 5 Chroma 5
2 SS Mg/L 5 6 pH 7.7
3 Ammonia nitrogen Mg/L 0 7 hardness Mmmol/l 115
4 Turbidity NTU 2 8 Conductivity μS/cm 830
表 6
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 163 4 含盐量 ‰ 11.5
2 SS mg/L 45 5 pH 8.2
3 浊度 NTU 4.6 6 电导率 µS/cm 9200
Table 6
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 163 4 Salt content ‰ 11.5
2 SS Mg/L 45 5 pH 8.2
3 Turbidity NTU 4.6 6 Conductivity μS/cm 9200
实施例 3 Example 3
5000吨/日造纸深度处理废水的净化及循环利用方法。 Purification and recycling method of 5000 tons/day papermaking advanced treatment wastewater.
所述造纸深度处理废水经测定，指标如表7 所示： The papermaking advanced treatment wastewater was measured, and the indicators are shown in Table 7:
表 7
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 265 4 色度 110
2 SS mg/L 33 5 pH 7.9
3 浊度 NTU 7 6 电导率 µS/cm 7700
Table 7
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 265 4 Chroma 110
2 SS Mg/L 33 5 pH 7.9
3 Turbidity NTU 7 6 Conductivity μS/cm 7700
造纸深度处理废水经供水泵12按250T/h 流速提取后，输入纳米催化电解机13 中，纳米催化电解水直接进入沉淀罐14 ，沉淀后经超滤膜***22 除去水中的固体杂质、浮游生物、细菌、胶体得净化废水。 The papermaking advanced treatment wastewater is extracted by the water supply pump 12 at a flow rate of 250 T/h, and then input into the nano catalytic electrolysis machine 13 The nano-catalyzed electrolyzed water directly enters the precipitation tank 14, and after being precipitated, the ultra-filtration membrane system 22 removes solid impurities, plankton, bacteria, and colloids in the water to purify the wastewater.
所述纳米催化电解的工作电压为5～6V ，电流强度为190～200mA/cm2 ，纳米催化电解产生初生态的氯[Cl] 、羟基和初生态氧 [O] ，以杀灭废水中微生物、氧化分解废水中的有机物，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后，经过浸没式超滤膜过滤分离***去除使水净化废水，测定SDI 为1.7 。The nano-catalytic electrolysis has an operating voltage of 5-6 V and a current intensity of 190-200 mA/cm 2 . The nano-catalytic electrolysis produces nascent chlorine [Cl], hydroxyl and nascent oxygen [O] to kill microorganisms in the wastewater. Oxidative decomposition of organic matter in the wastewater, and the suspension, colloid and charged particles in the wastewater form larger particles under the action of the electric field, and then the water purification wastewater is removed by the immersion ultrafiltration membrane filtration separation system, and the SDI is determined to be 1.7.
经过纳米催化电解单元和浸没式超滤膜过滤分离单元净化所得的净化废水经过经过截止阀41 、供水泵42 进入电渗析机43 中进行电渗析脱盐处理，分离成透析液（水）和浓缩液，透析液（水）经过透析液（水）出口和管道进入透析液（水）贮罐44 ，浓缩液经过浓缩水出口和管道进入浓缩水贮罐45 中。 The purified wastewater purified by the nano catalytic electrolysis unit and the immersion ultrafiltration membrane filtration separation unit passes through the shutoff valve 41 and the water supply pump 42. Entering the electrodialysis machine 43 for electrodialysis desalination treatment, separating into dialysate (water) and concentrate, dialysate (water) passing through the dialysate (water) outlet and pipe into the dialysate (water) storage tank 44 The concentrate enters the concentrated water storage tank 45 through the concentrated water outlet and the pipe.
所述电渗析***为填充电渗析***（ EDI ） ， 电渗析的工作条件是操作电压2.5 ㎏/㎝2 ，操作电压180 ～250V ，电流强度2～3A 。The electrodialysis system is a filled electrodialysis system (EDI), and the working conditions of electrodialysis are an operating voltage of 2.5 kg/cm 2 , an operating voltage of 180 to 250 V, and a current intensity of 2 to 3 A.
所述透析液和浓缩液的流速分别为200T/h 和50T/h ，废水的回收率为80.0% ，回用水的质量如表 8 所示，浓缩废水的指标如表9所示。 The flow rates of the dialysate and concentrate are 200T/h and 50T/h, respectively, and the recovery rate of wastewater is 80.0%. The quality of recycled water is shown in Table 8, and the indicators of concentrated wastewater are shown in Table 9.
表 8
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 32 5 色度 5
2 SS mg/L 未检出 6 pH 7.3
3 氨氮 mg/L 0.1 7 电导率 µS/cm 900
4 浊度 NTU 2 8 硬度 mmol/l 230
Table 8
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 32 5 Chroma 5
2 SS Mg/L not detected 6 pH 7.3
3 Ammonia nitrogen Mg/L 0.1 7 Conductivity μS/cm 900
4 Turbidity NTU 2 8 hardness Mmmol/l 230
表 9
序号 项目 单位 测定值 序号 项目 单位 测定值
1 CODCr mg/L 263 4 色度 16
2 SS mg/L 59 5 pH 8.1
3 浊度 NTU 6 6 电导率 µS/cm 15900
Table 9
Serial number project unit measured value Serial number project unit measured value
1 COD Cr Mg/L 263 4 Chroma 16
2 SS Mg/L 59 5 pH 8.1
3 Turbidity NTU 6 6 Conductivity μS/cm 15900
工业实用性Industrial applicability
本发明的技术方案废水经过处理，70～85% 可以再生循环利用，既减少废水排放，避免废水对环境污染，又减少水资源浪费，还可以使再生的循环水成本低于自来水价格，经济合理，产生较好的经济效益 ，具备良好的工业实用性。The technical solution of the present invention is treated with wastewater, 70-85% It can be recycled and reused, which not only reduces wastewater discharge, avoids environmental pollution of wastewater, but also reduces water waste. It can also make the cost of recycled recycled water lower than the price of tap water, economically reasonable and produce better economic benefits. With good industrial applicability.
序列表自由内容Sequence table free content

Claims (10)

  1. 基于电化学和电渗析技术的造纸废水循环利用装置，其特征在于设有： A papermaking wastewater recycling device based on electrochemical and electrodialysis technology, characterized in that:
    纳米催化电解***，纳米催化电解***设有截止阀、水泵、纳米催化电解机、缓冲沉淀罐和过滤机；截止阀的进口外接造纸废水二沉池排放口，水泵的进口接截止阀的出口，水泵的出口接纳米催化电解机的进口，纳米催化电解机的出口与缓冲沉淀罐的进口联接，缓冲沉淀罐的出口经过水泵与过滤机的进口联接；The nano catalytic electrolysis system has a shut-off valve, a water pump, a nano catalytic electrolysis machine, a buffer sedimentation tank and a filter; the inlet of the shut-off valve is externally connected to the discharge port of the second sedimentation tank of the papermaking wastewater, and the inlet of the water pump is connected to the outlet of the shut-off valve. The outlet of the water pump is connected to the inlet of the nano catalytic electrolysis machine, the outlet of the nano catalytic electrolysis machine is connected with the inlet of the buffer sedimentation tank, and the outlet of the buffer sedimentation tank is connected through the inlet of the water pump and the filter;
    浸没式超滤膜过滤分离***：浸没式超滤膜过滤分离***用于将纳米催化电解***所得的净化废水过滤、分离得透析水和浓缩水，浸没式超滤膜过滤分离***设有截止阀、浸没式超滤膜池、鼓风机、曝气器、超滤膜***、抽吸泵和透析水贮罐，所述截止阀的进口经进水管与纳米催化电解***的过滤机出口连接，截止阀出口接浸没式超滤膜池，超滤膜浸没在浸没式超滤膜池中的印染净化废水中，抽吸泵从超滤膜内侧将水负压抽吸过膜壁，产生的透析水通过抽吸泵收集到透析水贮罐用于进一步经过电渗析脱盐得供生产上循环利用的再生水；截止阀的进口接纳米催化电解***沉淀罐的出口，截止阀的出口接浸没式超滤膜池的进口，浸没式超滤膜池的出口依次经过抽吸泵、截止阀进入透析水贮罐；Immersion ultrafiltration membrane filtration separation system: immersion ultrafiltration membrane filtration separation system is used to filter and separate the purified wastewater obtained by the nano catalytic electrolysis system into dialysis water and concentrated water. The immersion ultrafiltration membrane filtration separation system is provided with a shut-off valve. , immersion ultrafiltration membrane tank, blower, aerator, ultrafiltration membrane system, suction pump and dialysis water storage tank, the inlet of the shut-off valve is connected with the filter outlet of the nano catalytic electrolysis system through the inlet pipe, the shut-off valve The outlet is connected to the immersion ultrafiltration membrane tank, and the ultrafiltration membrane is immersed in the printing and dyeing purification wastewater in the immersion ultrafiltration membrane tank, and the suction pump sucks the water negative pressure from the inner side of the ultrafiltration membrane through the membrane wall, and the generated dialysis water passes. The suction pump collects the dialysis water storage tank for further deionization by electrodialysis to obtain the reclaimed water for recycling in production; the inlet of the shut-off valve is connected to the outlet of the precipitation tank of the nano catalytic electrolysis system, and the outlet of the shut-off valve is connected to the immersion ultrafiltration membrane tank. The inlet of the submerged ultrafiltration membrane tank is sequentially passed through a suction pump and a shut-off valve into the dialysis water storage tank;
    超滤膜清洗***：超滤膜清洗***用于清洗超滤膜过滤分离***，超滤膜清洗***设有清洗液罐、反冲洗泵、截止阀和联接管道，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，截止阀的出口接超滤膜***；Ultrafiltration membrane cleaning system: The ultrafiltration membrane cleaning system is used to clean the ultrafiltration membrane filtration separation system. The ultrafiltration membrane cleaning system is provided with a cleaning liquid tank, a backwashing pump, a shut-off valve and a connecting pipe, and the outlet of the cleaning liquid tank is backwashed. The inlet of the pump, the outlet of the backwashing pump is connected to the inlet of the shut-off valve, and the outlet of the shut-off valve is connected to the ultrafiltration membrane system;
    电渗析***：电渗析***设有截止阀、供水泵、电渗析机、透析水贮罐和浓缩水贮罐；截止阀的进口接浸没式超滤膜过滤分离***透析水贮罐的出口，截止阀的出口接供水泵的进口，供水泵的出口接电渗析机的进口，电渗析机的透析水出口接透析水贮罐，电渗析的浓缩水出口接浓缩水贮罐。Electrodialysis system: electrodialysis system is equipped with a shut-off valve, water supply pump, electrodialysis machine, dialysis water storage tank and concentrated water storage tank; the inlet of the shut-off valve is connected to the outlet of the dialysis water storage tank of the immersion ultrafiltration membrane filtration separation system. The outlet of the valve is connected to the inlet of the water supply pump, the outlet of the water supply pump is connected to the inlet of the dialysis machine, the dialysis water outlet of the electrodialysis machine is connected to the dialysis water storage tank, and the concentrated water outlet of the electrodialysis is connected to the concentrated water storage tank.
  2. 如权利要求1所述的基于电化学和电渗析技术的造纸废水循环利用装置，其特征在于所述浸没式超滤膜过滤***的工作条件是：常温～45℃，工作压力为3～50kPa。The papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to claim 1, wherein the working condition of the immersed ultrafiltration membrane filtration system is: normal temperature to 45 ° C, and working pressure is 3 to 50 kPa.
  3. 如权利要求1所述的基于电化学和电渗析技术的造纸废水循环利用装置，其特征在于所述电渗析***选用倒极电渗析***、液膜电渗析***、填充电渗析***、双极性电渗析***或无极水电渗析***。The papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to claim 1, wherein the electrodialysis system comprises a reverse electrodialysis system, a liquid membrane electrodialysis system, a filled electrodialysis system, and a bipolarity. Electrodialysis system or stepless hydroelectric dialysis system.
  4. 如权利要求1所述的基于电化学和电渗析技术的造纸废水循环利用装置，其特征在于所述电渗析***的工作条件为0.5～3.0kg/cm2 ，操作电压为50～250V，电流强度为1～3A。The papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to claim 1, wherein the electrodialysis system has an operating condition of 0.5 to 3.0 kg/cm 2 and an operating voltage of 50 to 250 V, and current intensity. It is 1 to 3A.
  5. 基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于采用如权利要求1所述基于电化学和电渗析技术的造纸废水循环利用装置，所述循环利用方法包括以下步骤：A papermaking wastewater recycling method based on electrochemical and electrodialysis technology, characterized in that the papermaking wastewater recycling device based on electrochemical and electrodialysis technology according to claim 1 is used, and the recycling method comprises the following steps:
    1）纳米催化电解：将造纸废水经水泵提取后，输入纳米催化电解机中进行催化微电解后，输入多介质过滤机进行过滤，除去废水中因固体杂质、浮游生物、细菌、胶体得净化废水；1) Nano-catalytic electrolysis: After the papermaking wastewater is extracted by water pump, it is input into the nano-catalytic electrolysis machine for catalytic micro-electrolysis, and then input into a multi-media filter for filtration to remove waste water from the wastewater due to solid impurities, plankton, bacteria and colloids. ;
    2）浸没式超滤过滤：将经过纳米催化电解***系处理后的净化印染废水经管道流入浸没式超滤***过滤处理，得透析水；2) immersion ultrafiltration filtration: the purified printing and dyeing wastewater treated by the nano catalytic electrolysis system is filtered into a submerged ultrafiltration system through a pipeline to obtain dialysis water;
    3）电渗析：将经过步骤2）的浸没式超滤过滤处理所得的透析水经过水泵送入电渗析***，进行电渗析脱盐，得脱盐水和浓缩水。3) Electrodialysis: The dialysis water obtained by the immersion ultrafiltration filtration treatment of the step 2) is sent to an electrodialysis system by water pumping, and electrolyzed and desalted to obtain desalted water and concentrated water.
  6. 如权利要求5所述的基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于在步骤1）中，所述造纸废水的氯化钠含量为6‰～30‰，最好为0.6‰～1.3‰，氯化钠含量不够时添加工业氯化钠补充至6‰～50‰。The papermaking wastewater recycling method based on electrochemical and electrodialysis technology according to claim 5, wherein in the step 1), the papermaking wastewater has a sodium chloride content of 6 ‰ 30 ‰, preferably 0.6. ‰~1.3‰, when the content of sodium chloride is not enough, add industrial sodium chloride to 6‰～50‰.
  7. 如权利要求5所述的基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于在步骤1）中，所述纳米催化电解的工作电压为2～500V，两个极板间的电压差为2～18V ，最佳电压差为4～10V，电流密度为5～300 mA/cm2 ，最佳电流密度为50～200 mA/cm2 。The method for recycling papermaking wastewater based on electrochemical and electrodialysis technology according to claim 5, wherein in step 1), the working voltage of the nano catalytic electrolysis is 2 to 500 V, and the voltage between the two plates The difference is 2 to 18 V, the optimum voltage difference is 4 to 10 V, the current density is 5 to 300 mA/cm 2 , and the optimum current density is 50 to 200 mA/cm 2 .
  8. 如权利要求5所述的基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于在步骤1）中，所述过滤为砂滤、多介质过滤或微滤。The papermaking wastewater recycling method based on electrochemical and electrodialysis technology according to claim 5, wherein in the step 1), the filtering is sand filtration, multi-media filtration or microfiltration.
  9. 如权利要求5所述的基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于在步骤2）中，所述超滤***过滤处理的工作条件为：常温～45℃，工作压力为3～50kPa。The method for recycling papermaking wastewater based on electrochemical and electrodialysis technology according to claim 5, wherein in the step 2), the working condition of the filtration treatment of the ultrafiltration system is: normal temperature to 45 ° C, and the working pressure is 3 ~ 50kPa.
  10. 如权利要求5所述的基于电化学和电渗析技术的造纸废水循环利用方法，其特征在于在步骤3）中，所述电渗析***的工作条件为0.5～3.0kg/cm2，操作电压为50～250V，电流强度为1～3A。The papermaking wastewater recycling method based on electrochemical and electrodialysis technology according to claim 5, wherein in the step 3), the working condition of the electrodialysis system is 0.5 to 3.0 kg/cm 2 , and the operating voltage is 50 ~ 250V, the current intensity is 1 ~ 3A.
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CN111018203A (en) * 2019-12-27 2020-04-17 肇庆学院 Nickel-containing heavy metal wastewater resource recovery device
CN111268832A (en) * 2020-01-23 2020-06-12 天津大学 Separation and dehydration treatment method and device for high-organic-matter high-salt wastewater
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CN111268832B (en) * 2020-01-23 2022-03-25 天津大学 Separation and dehydration treatment method and device for high-organic-matter high-salt wastewater
CN112919683A (en) * 2021-02-07 2021-06-08 汪波 Advanced biochemical treatment system for papermaking sewage

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