CN114538572A - Method for treating reverse osmosis concentrated water by using electrochemical water treatment device - Google Patents
Method for treating reverse osmosis concentrated water by using electrochemical water treatment device Download PDFInfo
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- CN114538572A CN114538572A CN202210372819.5A CN202210372819A CN114538572A CN 114538572 A CN114538572 A CN 114538572A CN 202210372819 A CN202210372819 A CN 202210372819A CN 114538572 A CN114538572 A CN 114538572A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 132
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
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Classifications
-
- 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
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—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
-
- 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
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to the technical field of water treatment, and provides a method for reverse osmosis of concentrated water by using an electrochemical water treatment device, aiming at the problems of large occupied area, low filling density and low filtration efficiency of the existing conductive filter membrane water treatment technology. The method comprises the following steps: the reverse osmosis concentrated water is mixed with a high-grade oxidation medicament and then injected into an electrochemical water treatment device, after full aeration, the high-grade oxidation medicament diffuses on the surface of the membrane, the high-grade oxidation medicament generates free radicals or active substances between the electrode mesh and the conductive filter membrane, and macromolecular organic pollutants are oxidized and decomposed into micromolecular pollutants; the treated reverse osmosis concentrated water passes through the conductive filter membrane, is accumulated in the diversion bag and flows out of the membrane module along the structural gap of the flow passage spacing body under the pressure of the water outlet peristaltic pump; the electrochemical water treatment device comprises a cylindrical shell, a winding type membrane component and an aeration device. The device has small floor area and high filling density, and can quickly degrade refractory organic matters in a continuous circulation mode to reduce membrane pollution.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for treating reverse osmosis concentrated water by using an electrochemical water treatment device.
Background
The pesticide wastewater generated in the pesticide industry contains a large amount of organic matters and salt substances which are difficult to degrade. At present, many enterprises adopt a double-membrane method (ultrafiltration and reverse osmosis) to treat the produced pesticide wastewater. The high-salt-content concentrated water produced by the method adopts an evaporation crystallization means to recover water resources and separate and treat soluble salt solids. However, the reverse osmosis concentrated water of the agricultural chemical wastewater contains pollutants such as organic phosphorus and benzene. The residue of these organic contaminants causes the solid salts after crystallization to yellow and black, and can only be disposed of as hazardous waste.
For residual refractory organic pollutants in reverse osmosis concentrated water, the currently adopted methods include adsorption method, chemical oxidation method, ion exchange resin, advanced oxidation method and other technical means. However, the conventional process for removing the target pollutants from the reverse osmosis concentrated water has many problems due to the high salinity of the reverse osmosis concentrated water. For example, regeneration of an adsorbent by an adsorption method is difficult, a certain inhibitory effect of high-concentration salt ions on fenton reaction is obtained, secondary pollution is caused by a wet catalytic oxidation method, and running cost is high. Recent studies have shown that high concentrations of salt ions in reverse osmosis wastewater provide good conditions for electrochemical reactions in which organic contaminants can be effectively removed by electrochemical catalytic oxidation processes.
The electrochemical catalysis process is to remove target pollutants directly or indirectly near an electrode by controlling an oxidation-reduction way through voltage under the action of an external electric field. The key to controlling the performance of an electrochemical catalytic process is the electrode material. In recent years, conductive films have come to be used as electrode materials. The conductive film is a novel water treatment material combining film filtration and electrochemical catalysis. The conductive film can be used for processing water samples in a continuous flow mode. Compared with the traditional batch reaction mode, the mode compresses the catalytic oxidation reaction into the membrane pores, namely, the catalyst, the active oxygen and the pollutants are simultaneously limited in the membrane pores, and the active catalyst is exposed on the surface of the membrane and a plurality of active sites of the membrane pores. The method increases the concentration of local solution, enhances the mass transfer effect in the reaction process, and thus realizes the rapid degradation of trace pollutants in the water sample. Therefore, compared with the single membrane separation technology and the traditional electrochemical catalytic process, the electrocatalysis process has the advantages of no secondary pollution, simple equipment, good controllability, operation at normal temperature and normal pressure and the like, and is considered to be one of the most promising water treatment materials in the future. However, the existing conductive filter membrane water treatment technology has the problems of large occupied area, low filling density and low filtration efficiency of the device.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for treating reverse osmosis concentrated water using an electrochemical water treatment apparatus. The wound membrane module has the advantages of uniform liquid flow distribution and simple structure, reduces the occupied area of the device, improves the filling density of the membrane module, can realize the rapid degradation of refractory organic matters in a continuous flow mode by virtue of small aperture and large specific surface area, and reduces membrane pollution.
In order to realize the purpose, the invention is realized by the following technical scheme:
a method for reverse osmosis of concentrated water by using an electrochemical water treatment device comprises the following steps:
(1) connecting an electrode mesh and a conductive filter membrane of the electrochemical water treatment device with low-voltage direct current externally, mixing reverse osmosis concentrated water with a high-grade oxidation agent, and injecting the mixture into the electrochemical water treatment device from a water inlet by using a peristaltic pump;
(2) after the organic pollutants in the high-grade oxidation medicament and the reverse osmosis concentrated water are fully aerated, the high-grade oxidation medicament, the reverse osmosis concentrated water and the organic pollutants on the surface of the conductive filter membrane approach to the surface of the conductive filter membrane under the driving of the pumping action of a peristaltic pump, the high-grade oxidation medicament, the reverse osmosis concentrated water and the functional groups or defect positions on the surface of the conductive filter membrane are combined through diffusion on the surface of the membrane, under the action of an external electric field, the high-grade oxidation medicament generates free radicals or active substances with strong oxidation effect between a gap between an electrode mesh and the conductive filter membrane under the action of a catalyst, and the macromolecular organic pollutants are oxidized and decomposed into micromolecular pollutants;
(3) the treated reverse osmosis concentrated water enters the interior of the membrane module through the conductive filter membrane along with the pumping action of the peristaltic pump, is accumulated in the diversion bag, flows out of the membrane module along the structural gap of the flow passage spacing body under the pressure of the water outlet peristaltic pump and flows out of the water outlet;
the electrochemical water treatment device comprises a cylindrical shell, a winding type membrane component and an aeration device, wherein the winding type membrane component is arranged in the cylindrical shell, the cross section of the winding type membrane component is C-shaped, an electrode net, a conductive filter membrane and a diversion bag are sequentially arranged from an outer layer to an inner layer, the electrode net and the conductive filter membrane are separated by an insulating net, the electrode net is an anode, and the conductive filter membrane is a cathode; the flow guide bag is made of waterproof materials, the two sides of the conductive filter membrane and the flow guide bag are hermetically connected, a flow passage is arranged in the middle of the flow guide bag, a flow passage spacing body is arranged in the flow passage, and the flow passage spacing body is of a sheet structure with a concave-convex surface; a water inlet is formed in the side wall of the bottom of the cylindrical shell, a water outlet is formed in the top of the cylindrical shell, the water inlet is formed in one side of the electrode net, and the water outlet is formed in one side of the conductive filter membrane; the water inlet and the water outlet are respectively connected with a peristaltic pump; the aeration head of the aeration device is arranged at the bottom of the cylindrical shell.
Furthermore, the electrode net and the conductive filter membrane are externally connected with 0.5-10V low-voltage direct current.
Furthermore, the water inlet and the water outlet are respectively connected with a peristaltic pump for controlling the flow and the direction.
Furthermore, the surface of the flow passage spacing body is wavy and is parallel to the flow direction of sewage. Preferably, the flow channel spacer is a flexible membrane or a flexible mesh.
Further, the conductive filter membrane has a cut-off pore size of 1nm-1 μm, preferably 100-500nm.
Further, the conductive filter membrane is made of a flexible material, and is prepared by the following method: and loading the calcined carbon material and one of the metal and the metal oxide on an organic filter membrane serving as a framework material to obtain the conductive filter membrane.
Further, the carbon material is carbon nanotube, graphene or carbon black.
Further, the organic filter membrane is a polytetrafluoroethylene membrane, a polyamide membrane, a mixed cellulose ester membrane or a polyvinylidene fluoride membrane, and the pore size distribution range of the organic filter membrane is 0.2-5.0 μm.
Further, the metal or metal oxide is iron, manganese, nickel, copper, cobalt, platinum, silver or palladium and oxides thereof.
Further, the conductive filter membrane is loaded with metal or metal oxide by immersion, electroplating, calcination and the like.
Further, the electrode mesh is a titanium mesh, a stainless steel mesh, a ruthenium-plated metal mesh, an iridium-plated metal mesh, a thallium-plated metal mesh, or Ti/Sb-SnO2Electrodes or Ti/PbO2And an electrode.
Further, the distance between the conductive filter membrane and the electrode mesh is 0.3-5mm, and preferably, the distance between the conductive filter membrane and the electrode mesh is 0.5 mm.
Furthermore, the diversion bag is made of a flexible material made of PE, PP or CPP.
Furthermore, the material of tube-shape shell is organic glass, silica gel, stainless steel or carbon steel.
Further, the cross section of the cylindrical shell is circular or square.
Further, the higher oxidizing agent is hydrogen peroxide, persulfate or hypochlorite, the use concentration of the higher oxidizing agent is 1-100mM, and further the use concentration of the higher oxidizing agent is 5-30 mM.
Further, the aeration gas is air or oxygen, and the aeration intensity is 5-25m3/m2H, preferably 15m3/m2·h。
Further, the hydraulic retention time is 2-120 min.
The advanced treatment method of the invention takes a conductive filter membrane and a heterogeneous Fenton-like water treatment device as a core, utilizes an electrode plate as an anode and a conductive filter membrane as a cathode, and fills carbon materials with catalytic performance between the conductive filter membranes to form a coupling system of the conductive filter membrane and the heterogeneous Fenton. The water inlet of the water treatment device is arranged on one side of the anode plate, and the water outlet of the water treatment device is arranged on one side of the cathode filter membrane. The high-grade oxidizing agent is quickly coated on the catalytic filler and the conductive filter membraneThe fast catalytic decomposition is carried out to generate strong oxidant OH free radicals, and organic pollutants on the surface of the membrane and in the reverse osmosis concentrated water are oxidized and degraded. The antiphlogistic in the inlet water is removed through heterogeneous Fenton oxidation and membrane interception and filtration, and is discharged from the water outlet. In particular, if no higher oxidizing agent is added, the oxygen provided by aeration can be reduced to H in situ on the catalytic filler and the conductive filter membrane2O2And the function of removing pollutants through oxidation is achieved.
Has the advantages that:
1. the membrane component part of the electrochemical water treatment device adopts a winding membrane component structure, and compared with the characteristics of large floor area and low filling density of a common plate-frame type membrane component, the electrochemical water treatment device has the advantages of simple structure, high filling density and higher filtering efficiency than a plate-frame membrane. The invention can realize larger unit membrane area proportion in a limited device volume and improve the sewage removal efficiency in unit time. Compared with the common filter element structure, the filter element structure can be reused to reduce the replacement times of materials, thereby realizing long-acting and low-consumption treatment of organic pollutants.
2. The application of the conductive filter membrane enables electrochemistry and membrane separation to be coupled, and the membrane separation can protect the electrode so as to reduce pollution of particles and colloidal substances in sewage and prolong the service life of the electrode; in addition, the mass transfer effect of the electrode near the electrochemical electrode can be increased in the membrane separation process, so that reverse osmosis concentrated water can be rapidly contacted with free radicals such as hydroxyl free radicals and superoxide free radicals when passing through the membrane holes, and the electrochemical efficiency is improved.
3. The treatment method combines the conductive filter membrane with a heterogeneous Fenton-like oxidation method, takes the metal filter screen as an anode, the conductive filter membrane as a cathode, and salts in the reverse osmosis concentrated water as electrolyte, thereby avoiding secondary pollution possibly caused by adding the electrolyte. After the power is switched on, the advanced oxidation agent and the dissolved oxygen between the electrodes can quickly generate free radicals with strong oxidation effects such as hydroxyl free radicals and the like, so that an electric field is formed to strengthen heterogeneous Fenton-like reaction, and organic pollutants in the reverse osmosis concentrated water can be oxidized and degraded.
Drawings
FIG. 1 is a schematic view showing a structure of a wound membrane module of an electrochemical water treatment apparatus according to example 1;
FIG. 2 is a schematic view showing the overall structure of an electrochemical water treatment apparatus according to example 1;
FIG. 3 is a schematic view of a spacer model of a flow channel of an electrochemical water treatment device according to example 1;
FIG. 4 is a graph showing the degradation effect of the reverse osmosis concentrated water according to examples 1 to 3, wherein the abscissa represents the degradation time and the ordinate represents the residual rate of organic contaminants.
Reference numerals:
1. the device comprises an electrode net, 2 a insulation net, 3 a conductive filter membrane, 4 a flow guide bag, 5 a flow channel spacing body, 6 a water inlet peristaltic pump, 7 a water inlet, 8 an aeration pump, 9 a water outlet, 10 a direct current power supply, 11 a water outlet peristaltic pump, 12 and an aeration head.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
Example 1
The reverse osmosis concentrated water is treated by utilizing a winding type electrochemical water treatment device, and the main salt ions in the reverse osmosis concentrated water have SO4 2-(100mg·L-1)、Cl-(350mg·L-1)、Ca2+、Na+、Mg2+、K+And metronidazole (10 mg. L)-1) A contaminant.
The winding type electrochemical water treatment device is coupled with the conductive filter membrane and is integrated with the heterogeneous Fenton-like membrane, and comprises a reactor body and a winding type membrane component. As shown in FIGS. 1 and 2, the apparatus comprises a cylindrical housing of 70X 110cm, a wound membrane module disposed in the cylindrical housing, and an aeration apparatus. The cross section of the winding type membrane component is C-shaped, and comprises an electrode mesh 1, an insulating mesh 2, a conductive filter membrane 3, a flow channel spacing body 5 and a diversion bag 4. The electrode net 1 is an anode and is externally connected with the anode of a direct current power supply 10 through a lead, the conductive microfiltration membrane 3 is a cathode and is externally connected with the cathode of the direct current power supply 10 through a lead. The electrode net 1 and the conductive filter membrane 3 are separated by the insulating net 2, and the distance between the electrode net 1 and the conductive filter membrane 3 is 0.5 mm. The conductive filter membrane has a cut-off pore size of 100 nm. The diversion bag 4 is made of waterproof materials, the two sides of the conductive filter membrane 3 and the diversion bag 4 are hermetically connected, a flow passage is arranged in the middle of the diversion bag, and the flow passage spacing body 5 is arranged in the flow passage.
The flow channel spacer 5 is a sheet-like flexible net with a concave-convex surface, as shown in fig. 3.
And a water inlet 7 is formed in the side wall of the bottom of the cylindrical shell, a water outlet 9 is formed in the top of the cylindrical shell, the water inlet 7 is formed in one side of the electrode net, the water outlet 9 is formed in one side of the conductive filter membrane, and the water inlet 7 and the water outlet 9 are respectively connected with the peristaltic pump. The aeration head 12 of the aeration device is arranged at the bottom of the cylindrical shell, and the aeration rate is 1.5 L.h-1。
The conductive filter membrane is prepared by the existing method: and loading the calcined carbon material and one of the metal and the metal oxide on an organic filter membrane serving as a framework material to obtain the conductive filter membrane. The carbon material is carbon nanotube, graphene or carbon black. The organic filter membrane is a polytetrafluoroethylene membrane, a polyamide membrane, a mixed cellulose ester membrane or a polyvinylidene fluoride membrane, and the pore size distribution range of the organic filter membrane is 0.2-5.0 mu m. The metal or metal oxide is iron, manganese, nickel, copper, cobalt, platinum, silver or palladium and oxides thereof. The conductive filter membrane is loaded with metal or metal oxide by immersion, electroplating, calcination and the like.
The electrode mesh is preferably a titanium mesh, a stainless steel mesh, ruthenium-plated, iridium, thallium metal mesh, Ti/Sb-SnO2Electrodes or Ti/PbO2And an electrode.
The material of the cylindrical shell is preferably organic glass, silica gel, stainless steel or carbon steel.
When the device runs, the wound membrane component is vertically placed, the electrode mesh and the conductive filter membrane of the electrochemical water treatment device are externally connected with low-voltage direct current, and a constant 50mA current is applied by a low-voltage direct current power supply. Mixing 250ml reverse osmosis concentrated water with advanced oxidation agent hydrogen peroxide, injecting into the electrochemical water treatment device from a water inlet 7 by a water inlet peristaltic pump 6, wherein the concentration of the mixed hydrogen peroxide solution is 5 mmol.L-1，The flow rate was 1.5 mL/min-1The air blown by the aeration head 12 forms a uniform water-air mixture with the influent wastewater.
After the organic pollutants in the advanced oxidation agent and the reverse osmosis concentrated water are fully aerated, the advanced oxidation agent and the organic pollutants in the reverse osmosis concentrated water approach the surface of the conductive filter membrane 3 under the driving of the pumping action of the water inlet peristaltic pump, through diffusion on the surface of the membrane, the hydrogen peroxide, the reverse osmosis concentrated water and functional groups or defect positions on the surface of the conductive filter membrane are combined, under the action of an external electric field, the hydrogen peroxide generates free radicals or active substances with strong oxidation effect between gaps of the electrode mesh 1 and the conductive filter membrane 3 under the action of a catalyst, and the macromolecular organic pollutants are oxidized and decomposed into micromolecular pollutants.
The treated reverse osmosis concentrated water enters the interior of the membrane module through the conductive filter membrane along with the pumping action of the peristaltic pump, is accumulated in the diversion bag, and flows out of the membrane module along the structural gaps of the flow passage spacing bodies under the pressure of the water outlet peristaltic pump and flows out of the water outlet.
And then, after twice circulation, the degradation rate of the nitrazole in the reverse osmosis concentrated water reaches 84 percent.
Example 2
The electrochemical water treatment device of example 1 was used to treat reverse osmosis concentrated water, and the salt ions mainly contained in the simulated reverse osmosis concentrated water had SO4 2-(100mg·L-1)、Cl-(350mg·L-1)、Ca2+、Na+、Mg2+、K+And metronidazole (10 mg. L)-1) A contaminant.
The processing steps differ from example 1 in that: the advanced oxidation medicament adopts sodium persulfate, 250ml of simulated reverse osmosis concentrated water is mixed with sodium persulfate solution, and the concentration of the mixed sodium persulfate solution is 10 mmol.L-1Sodium persulfate is catalyzed on the carbon nano tube conductive filter membrane 3 loaded with cerium oxide to generate hydroxyl free radicals, sulfate free radicals and the like, and organic pollutants in the reverse osmosis concentrated water are degraded in an oxidizing mode. And then, through twice circulation, the removal efficiency of the nitre in the reverse osmosis concentrated water reaches 85 percent.
Example 3
The electrochemical water treatment device of example 1 was used to treat reverse osmosis concentrated water, and the salt ions mainly contained in the simulated reverse osmosis concentrated water had SO4 2-(250mg·L-1)、Cl-(132mg·L-1)、Ca2+、Na+、Mg2+、K+And metronidazole (10 mg. L)-1) A contaminant.
The processing steps differ from example 1 in that: the high-grade oxidation agent adopts sodium hypochlorite and 250ml of simulated reverse osmosis concentrated water mixed sodium hypochlorite solution, and the concentration of the mixed sodium hypochlorite solution is 10 mmol.L-1. And then, through twice circulation, the removal efficiency of the nitre in the reverse osmosis concentrated water reaches 91 percent.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A method for reverse osmosis of concentrated water by using an electrochemical water treatment device is characterized by comprising the following steps:
(1) connecting an electrode mesh and a conductive filter membrane of the electrochemical water treatment device with low-voltage direct current externally, mixing reverse osmosis concentrated water with a high-grade oxidation agent, and injecting the mixture into the electrochemical water treatment device from a water inlet by using a peristaltic pump;
(2) after the organic pollutants in the high-grade oxidation medicament and the reverse osmosis concentrated water are fully aerated, the high-grade oxidation medicament, the reverse osmosis concentrated water and the organic pollutants on the surface of the conductive filter membrane approach to the surface of the conductive filter membrane under the driving of the pumping action of a peristaltic pump, the high-grade oxidation medicament, the reverse osmosis concentrated water and the functional groups or defect positions on the surface of the conductive filter membrane are combined through diffusion on the surface of the membrane, under the action of an external electric field, the high-grade oxidation medicament generates free radicals or active substances with strong oxidation effect between a gap between an electrode mesh and the conductive filter membrane under the action of a catalyst, and the macromolecular organic pollutants are oxidized and decomposed into micromolecular pollutants;
(3) the treated reverse osmosis concentrated water enters the interior of the membrane module through the conductive filter membrane along with the pumping action of the peristaltic pump, is accumulated in the diversion bag, flows out of the membrane module along the structural gap of the flow passage spacing body under the pressure of the water outlet peristaltic pump and flows out of the water outlet;
the electrochemical water treatment device comprises a cylindrical shell, a membrane component and an aeration device, wherein the membrane component is a winding membrane component, is arranged in the cylindrical shell, has a C-shaped cross section, and sequentially comprises an electrode net, a conductive filter membrane and a diversion bag from an outer layer to an inner layer, the electrode net and the conductive filter membrane are separated by an insulating net, the electrode net is an anode, and the conductive filter membrane is a cathode; the flow guide bag is made of waterproof materials, the two sides of the conductive filter membrane and the flow guide bag are hermetically connected, a flow passage is arranged in the middle of the flow guide bag, a flow passage spacing body is arranged in the flow passage, and the flow passage spacing body is of a sheet structure with a concave-convex surface; a water inlet is formed in the side wall of the bottom of the cylindrical shell, a water outlet is formed in the top of the cylindrical shell, the water inlet is formed in one side of the electrode net, and the water outlet is formed in one side of the conductive filter membrane; the water inlet and the water outlet are respectively connected with a peristaltic pump; the aeration head of the aeration device is arranged at the bottom of the cylindrical shell.
2. The method of claim 1, wherein the surface of the flow channel spacer is corrugated.
3. The method of claim 1, wherein the flow channel spacer is a flexible material.
4. The method of claim 1, wherein the conductive filter membrane has a cut-off pore size of 1nm to 1 μm.
5. The method according to claim 1, wherein the conductive filter membrane is made of a flexible material and is prepared by the following method: and loading the calcined carbon material and one of the metal and the metal oxide on an organic filter membrane serving as a framework material to obtain the conductive filter membrane.
6. The method of claim 5, wherein the carbon material is carbon nanotubes, graphene, or carbon black; the organic filter membrane is a polytetrafluoroethylene membrane, a polyamide membrane, a mixed cellulose ester membrane or a polyvinylidene fluoride membrane, and the pore size distribution range of the organic filter membrane is 0.2-5.0 mu m; the metal or metal oxide is iron, manganese, nickel, copper, cobalt, platinum, silver or palladium and oxides thereof; the conductive filter membrane is loaded with metal or metal oxide by means of immersion, electroplating or calcination.
7. The method of claim 6, wherein the electrode mesh is a bendable titanium mesh, a stainless steel mesh, a ruthenium-plated metal mesh, an iridium-plated metal mesh, a thallium-plated metal mesh, Ti/Sb-SnO2Electrodes or Ti/PbO2And an electrode.
8. The method of claim 7, wherein the conductive filter membrane is spaced from the electrode mesh by 0.3-5 mm.
9. The method of claim 8, wherein the higher oxidizing agent is hydrogen peroxide, persulfate, or hypochlorite, and the dosage concentration of the higher oxidizing agent is 1-100 mM.
10. The method of claim 8, wherein the flow-through bag is a flexible material of PE, PP or CPP.
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