CN107892363B - Water treatment device and method for synchronously generating electricity and converting high-valence metal ions - Google Patents
Water treatment device and method for synchronously generating electricity and converting high-valence metal ions Download PDFInfo
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- 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
- C02F1/46176—Galvanic cells
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/46135—Voltage
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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
- 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
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2303/00—Specific treatment goals
- C02F2303/10—Energy recovery
Abstract
The inventionDiscloses a water treatment device and a water treatment method for synchronously generating electricity and converting high-valence metal ions. The device includes an electrochemical system; the electrochemical system comprises at least one galvanic cell; each galvanic cell comprises: the active metal anode is made of metal with a negative standard electrode potential; a porous catalytic cathode comprising a porous electrically conductive substrate; a porous dielectric separator layer separating the active metal anode and the porous catalytic cathode. The device and the method have the advantages of convenient operation, low requirements on raw materials and equipment, good effect of treating water polluted by high-valence heavy metals (such as chromium, vanadium and the like), removal rate of heavy metal ions of more than 90 percent, and electricity generation power density of 810W/m3Provides a new method for realizing synchronous electricity generation and removing high-valence heavy metal ions in water in industrialization and large scale.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a water treatment device and method for synchronously generating electricity and converting high-valence metal ions.
Background
With the continuous development of the industrialization process, the industrial wastewater discharge attracts more and more attention. In the process of exploring the response to industrial pollution, people are not only limited to the removal and degradation of pollutants, but also require the realization of energy or resource recovery while realizing the purification of wastewater. Chemicals in wastewater are a potential source of energy and materials. Among these, the redox species in wastewater account for a considerable proportion, especially the high-valence metal compounds. In addition, high oxidation state metal compounds tend to exhibit high migratory and hazardous properties, such as high-valent radioactive metals, e.g., U (VI), Tc (VII), Np (V) and Pu (VI), and carcinogenic heavy metals, Cr (VI) and V (V), etc. Therefore, the environment hazard can be reduced to the maximum extent by reducing the oxidation state of the catalyst to a low oxidation state. The conventional techniques mainly include chemical reduction, biological reduction, electrochemical reduction and the like. Although the method can effectively relieve the problems of toxicity and mobility, a large amount of medicament and energy are also input, if the energy contained in the wastewater can be recovered, a large amount of water treatment cost can be saved, and certain social and economic benefits can be obtained.
From the oxidation-reduction potential analysis, it is found that the high-valence metal ions have a high oxidation-reduction potential. Electrochemical techniques can be used to treat and recover heavy metals, while it is also possible to capture the energy in the wastewater and convert it into electrical energy. In the actual water treatment process, the electrolytic cell electrolysis technology can reduce or oxidize heavy metal ions in water, but the process consumes electric energy, so that the wastewater treatment cost is increased; the primary battery micro-electrolysis technology has high treatment efficiency, but cannot collect the energy in the wastewater. If a proper electrochemical energy recovery device is constructed by utilizing the principle of a primary battery, high-valence metal ions in the wastewater are used as an electron acceptor, and a substance with a lower oxidation-reduction potential is selected as an electron donor, so that the energy contained in the high-valence metal ions can be converted, and the toxicity of the metal ions is reduced.
Chinese patent No. 201110386545.7 discloses a device for removing metal ions while generating electricity and a method thereof, the device is divided into an anode chamber and a cathode chamber, the middle is an ion or proton exchange membrane, the anode chamber is an aqueous solution of reducing substances, the cathode chamber is high-valence metal ions, but the ion or proton exchange membrane is high in price, is easy to age in wastewater, and is not suitable for large-scale popularization and application.
Disclosure of Invention
The invention aims to provide a water treatment device and a water treatment method for synchronously generating electricity and converting high-valence metal ions, which are convenient to operate, have low requirements on raw materials and equipment, can treat waste water polluted by high-valence heavy metals, have low cost and good effect and are convenient to practically apply.
The invention provides a water treatment device for synchronously generating electricity and converting high-valence metal ions; it comprises an electrochemical system; the electrochemical system comprises at least one galvanic cell; each galvanic cell comprises:
the active metal anode is made of metal with a negative standard electrode potential;
a porous catalytic cathode comprising a porous electrically conductive substrate;
a porous dielectric separator layer separating the active metal anode and the porous catalytic cathode.
In the above water treatment apparatus, the active metal anode may be made of inexpensive aluminum, iron or zinc.
In the above water treatment device, the porosity of the porous catalytic cathode may be 30% to 90% (e.g., 60%). The thickness of the porous catalytic cathode can be 1-10 mm (e.g., 5 mm).
The porous conductive substrate may be graphite felt (graphite fiber felt), carbon cloth, carbon paper, nickel foam, copper foam, or titanium foam.
The porous catalytic cathode may further comprise a catalyst supported on the porous electrically conductive substrate. The catalyst may be polyaniline, polypyrrole, palladium, gold, or platinum. The loading capacity of the catalyst can be 0-50 mg/cm2E.g. 10mg/cm2。
In the above water treatment device, the porous dielectric isolation layer may be made of cheap polyurethane, nylon or polypropylene fiber, and is a porous hydrophilic layer.
The porosity of the porous dielectric isolation layer can be 40% -70% (such as 70%), and the pore diameter can be 0.1-1.2 μm (such as 0.8 μm).
The porous dielectric spacer layer may have a thickness of 1 to 5mm (e.g., 2 mm).
In the above water treatment device, the connection mode of the electrodes in the electrochemical system may be a single-pole connection or a multi-pole connection;
the number of the primary battery units is 1, the connection mode is single-pole connection, and the method specifically comprises the following steps: the active metal anode and the porous catalytic cathode in the primary battery unit are connected with an external resistor or an energy storage device I through a lead;
the number of the primary battery units is more than or equal to 2, the connection mode is a bipolar connection mode, and the method specifically comprises the following steps: the active metal anode in the first primary battery unit and the porous catalytic cathode in the last primary battery unit are connected with an external resistor or an energy storage device I through leads; the porous catalytic cathode in the first primary battery unit is connected with the active metal anode in the second primary battery unit through a lead, the porous catalytic cathode in the second primary battery unit is connected with the active metal anode in the third primary battery unit through a lead, and the like; each of the cells is separated from another cell by the porous dielectric spacer.
The water treatment device also comprises a raw water storage tank, a pretreatment unit, a pH regulation unit, a precipitation separation unit and an energy storage device II; the raw water storage tank, the pretreatment unit, the pH regulation unit, the electrochemical system and the precipitation separation unit are sequentially connected; the pretreatment unit is used for carrying out primary filtration on raw wastewater; the energy storage device II is connected with the electrochemical system and is used for storing electric energy generated in the electrochemical system; the precipitation separation unit is used for coprecipitating the obtained low-valence metal ions by adjusting the pH value of the wastewater.
The invention further provides a method for realizing synchronous electricity generation and high-valence metal ion conversion in wastewater by using the water treatment device, which comprises the following steps: and the wastewater containing high-valence metal ions passes through the porous catalytic cathode, the active metal anode loses electrons and transmits the electrons to the porous catalytic cathode through an external resistor and/or an energy storage device I, and the electrons obtained by the high-valence metal ions on the surface of the porous catalytic cathode are reduced into low-valence metal ions, so that the synchronous electricity generation and the conversion of the high-valence metal ions are completed.
In the above method, the high valence metal ion can be Cr (VI), V (V), U (VI), Tc (VII), Np (V) or Pu (VI).
The entering direction of the wastewater containing the high valence metal ions can be parallel to the electrode.
In the above method, the high valence metal ions may be reduced under the action of a catalyst supported on the surface of the porous catalytic cathode. The reduction of the high valence metal ions is realized by the direct reduction of a catalyst on the surface of the porous catalytic cathode (the catalyst indirectly transfers electrons to the high valence metal ions through the change of the valence state of the catalyst so as to reduce the high valence metal ions), or the indirect reduction of the generated active species (the electrons reduce hydrogen ions to generate hydrogen radicals); the presence of the catalyst can accelerate the reduction process, so that electrons are more easily transferred to high-valence metal ions. The active metal anode loses electrons and converts itself to free ions.
In the method, the reduction rate of the high-valence metal ions is further controlled by adjusting the size of the external resistor and controlling the voltage and the current. The energy storage device I can store the generated electric energy.
The method also comprises the steps of sequentially carrying out primary filtration on raw wastewater and adjusting the pH value before reducing the high-valence metal ions.
The method also comprises the step of coprecipitating the obtained low-valence metal ions by adjusting the pH value of the wastewater after reducing the high-valence metal ions.
The invention has the following beneficial effects:
(1) the water treatment device takes active metal as an anode, takes a porous conductive material loaded catalyst as a cathode, wastewater containing high-valence metal ions passes through the porous catalytic cathode, the active metal anode loses electrons and transmits the electrons to the porous catalytic cathode through a connected resistor, the electrons obtained by the high-valence metal ions on the surface of the porous catalytic cathode are reduced into low-valence metal ions, and the synchronous electricity generation and the conversion of the high-valence metal ions are completed.
(2) The device and the method have the advantages of convenient operation, low requirements on raw materials and equipment, good effect of treating water polluted by high-valence heavy metals (such as chromium, vanadium and the like), removal rate of heavy metal ions of more than 90 percent, and electricity generation power density of 810W/m3Provides a new method and a new application for realizing synchronous electricity generation and removing high-valence heavy metal ions in water in industrialization and large scale.
Drawings
FIG. 1 is a schematic structural view of a water treatment apparatus for simultaneously generating electricity and reducing high-valence heavy metal ions according to the present invention.
In fig. 1, each representation is as follows:
① raw water storage tank, ② pretreatment unit, ③ pH adjustment unit, ④ electrochemical system, ⑤ energy storage device II, ⑥ precipitation separation unit.
FIG. 2 is a schematic view showing the structure of an electrochemical system (unipolar type) in the water treatment apparatus for simultaneously generating electricity and reducing heavy metal ions having high valences in example 1.
FIG. 3 is a schematic view showing the structure of an electrochemical system (bipolar type) in the water treatment apparatus for simultaneously generating electricity and reducing heavy metal ions having high valence in example 2.
Each of fig. 2 and 3 is labeled as follows: 1 active metal anode, 2 porous dielectric isolation layer, 3 porous catalytic cathode, 4 external connecting wire, 5 external connecting resistance (or energy storage device I).
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The catalyst polyaniline on the porous catalytic cathode graphite felt in the following examples is prepared by a constant-current multi-step electrodeposition method, which comprises the following steps: placing porous conductive matrix graphite felt in electrolyte (0.5M aniline monomer, 1M perchloric acid solution), and first measuring current density at 2.0mA cm-2Deposition for 10min followed by 1.0mA cm-2Depositing for 2hr, and depositing for 0.5mAcm-2Depositing for 2hr to obtain polyaniline loaded on graphite felt (loading amount is 10 mg/cm)2)。
As shown in FIG. 1, the water treatment device comprises a raw water storage tank ①, a pretreatment unit ②, a pH adjusting unit ③, an electrochemical system ② 2, an energy storage device II ② 1 and a precipitation separation unit, wherein the raw water storage tank ①, the pretreatment unit ② 0, the pH adjusting unit ③, the electrochemical system ④ and the precipitation separation unit ② 3 are sequentially connected, the pretreatment unit ② is used for primary filtration of raw wastewater, the energy storage device II ⑤ is connected with the electrochemical system ④ and used for storing electric energy generated in the electrochemical system, and the precipitation separation unit ⑥ is used for coprecipitation of low-valence metal ions obtained by adjusting the pH value of wastewater.
As shown in fig. 2 and 3, the electrochemical system ④ includes at least one primary cell, each primary cell including:
the material is an active metal anode 1 with a standard electrode potential being a negative value (such as aluminum, iron or zinc);
the porous conductive substrate (such as graphite felt, carbon cloth, carbon paper, foamed nickel, foamed copper or foamed titanium) and the loading amount loaded on the porous conductive substrate are 0-50 mg/cm2The catalyst (such as polyaniline, polypyrrole, palladium, gold or platinum) of (3) constitutes a porous catalytic cathode 3 with a porosity of 30-90% and a thickness of 1-10 mm;
a porous dielectric isolation layer 2 with porosity of 40% -70%, pore diameter of 0.1-1.2 μm and thickness of 1-5 mm, which separates the active metal anode and the porous catalytic cathode;
the electrodes in the electrochemical system are connected in a monopolar or a bipolar manner.
The number of the primary battery units is 1, the connection mode is single-pole connection, and the method specifically comprises the following steps: the active metal anode and the porous catalytic cathode in the primary battery unit are connected with an external resistor or an energy storage device I through a lead;
the number of the primary battery units is more than or equal to 2, the connection mode is repolarization connection, and the method specifically comprises the following steps: the active metal anode in the first primary battery unit and the porous catalytic cathode in the last primary battery unit are connected with an external resistor or an energy storage device I through leads; the porous catalytic cathode in the first primary battery unit is connected with the active metal anode in the second primary battery unit through a lead, the porous catalytic cathode in the second primary battery unit is connected with the active metal anode in the third primary battery unit through a lead, and the like; each of the cells is separated from another cell by the porous dielectric spacer.
The use method comprises the following steps that wastewater containing high-valence metal ions in a raw water storage tank ① sequentially enters a pretreatment unit ② to primarily filter the wastewater, a pH value is adjusted by a pH adjusting unit ③ and then enters an electrochemical system ④, in the electrochemical system ④, the wastewater passes through a porous catalytic cathode from a position a along the direction of an electrode, an active metal anode loses electrons and transmits the electrons to the porous catalytic cathode through an external resistor and/or an energy storage unit, the high-valence metal ions obtain electrons on the surface of the porous catalytic cathode under the action of a catalyst and are reduced into low-valence metal ions, the reduced wastewater is discharged from a position b, the wastewater discharged from the electrochemical system ④ enters a precipitation separation unit ⑥, the obtained low-valence metal ions are subjected to coprecipitation by adjusting the pH value of the reduced wastewater, the effect of separation from water is achieved, the wastewater is discharged, and the conversion of synchronous electricity generation and the high-valence metal ions can be completed.
Example 1 Water treatment apparatus for Simultaneous Electricity Generation and reduction of high valent heavy Metal ions (unipolar type)
Structure of water treatment device
As shown in FIG. 2, the electrochemical system ④ of the water treatment device for synchronously generating electricity and converting high-valence metal ions in the embodiment comprises 1 primary battery unit, wherein the primary battery unit comprises:
an active metal anode 1 made of an iron plate with the thickness of 3 mm;
the graphite felt consists of a porous conductive matrix graphite felt (the average diameter of graphite fibers is 15 microns) and the loading amount of graphite felt loaded with the graphite felt is 10mg/cm2The catalyst polyaniline forms a porous catalytic cathode 3 with the thickness of 5mm and the porosity of 60 percent;
a porous dielectric isolation layer 2 composed of polypropylene fibers with porosity of 70%, pore diameter of 0.8 μm and thickness of 2mm, which separates an active metal anode 1 and a porous catalytic cathode 3;
the active metal anode 1 and the porous catalytic cathode 3 are connected with an external resistor 5 with the resistance of 10 omega through a lead 4.
Secondly, the wastewater is treated by utilizing the water treatment device
1. Treating the waste water containing 10 mg/L hexavalent chromium
The water treatment device is used for treating the waste water containing 10 mg/L hexavalent chromium, and comprises the following steps:
regulating pH value of waste water containing 10 mg/L hexavalent chromium ions to 2.0, making the waste water pass through porous catalytic cathode along electrode direction (arrow direction) at flow rate of 0.1cm/s for 50s, output voltage of 0.4V, making active metal anode lose electrons and transfer the electrons to porous catalytic cathode by means of external resistor, under the action of catalyst the hexavalent chromium can be obtained on the surface of porous catalytic cathode and reduced into low-valence chromium (trivalent), regulating pH value of waste water to 8.0 to make low-valence metal ions (equivalent trivalent chromium and trivalent iron) implement coprecipitation, removing precipitate from waste water so as to implement synchronous electricity production and conversion of hexavalent chromium ions, and can obtain hexavalent chromium removal rate of 90%, and its electricity-producing power density is 6.4W/m2. The electricity generation power density formula: p ═ UI/a ═ 0.4V ×. 0.04A/0.0025m2＝6.4W/m2Where U is the output voltage, I is the current, and A is the area of the cathode.
2. Treating waste water containing 100 mg/L hexavalent chromium
The water treatment device is used for treating the hexavalent chromium wastewater containing 100 mg/L, and comprises the following steps:
regulating pH value of waste water containing 100 mg/L hexavalent chromium ions to 1.5, making the waste water pass through porous catalytic cathode 3 along electrode direction (arrow head) at flow rate of 0.1cm/s for 50s, output voltage of 0.65V, making active metal anode lose electrons and transferring the electrons to porous catalytic cathode by means of external resistor, under the action of catalyst making hexavalent chromium obtain electrons on the surface of porous catalytic cathode and reduce them into low-valence chromium (trivalent chromium), regulating pH value of waste water to 8.0 making low-valence metal ions (equivalent trivalent chromium and trivalent iron) implement coprecipitation, removing precipitate from waste water so as to implement synchronous electricity production and conversion of hexavalent chromium ionsUp to 95 percent, and the power density of electricity generation is 16.9W/m2. The electricity generation power density calculation formula is as follows: p ═ UI/a ═ 0.65V ×. 0.065A/0.0025m2＝16.9W/m2Where U is the output voltage, I is the current, and A is the area of the cathode.
Example 2 Water treatment apparatus for Simultaneous Electricity Generation and reduction of high valent heavy Metal ions (multipole type)
Structure of water treatment device
As shown in FIG. 3, the electrochemical system ④ of the water treatment device for synchronously generating electricity and converting high-valence metal ions in the embodiment comprises 6 primary battery units, wherein each primary battery unit comprises:
an active metal anode 1 made of an iron plate with the thickness of 3 mm;
the graphite felt consists of a porous conductive matrix graphite felt (the average diameter of graphite fibers is 15 mu m) and the loading amount of graphite felt loaded is 10mg/cm2The catalyst polyaniline forms a porous catalytic cathode 3 with the thickness of 5mm and the porosity of 60 percent;
a porous dielectric isolation layer 2 composed of polypropylene fibers with porosity of 70%, pore diameter of 0.8 μm and thickness of 2mm, which separates an active metal anode 1 and a porous catalytic cathode 3;
an active metal anode 1 in a first primary battery unit and a porous catalytic cathode 3 in a sixth primary battery unit are connected with an external resistor 5 with the resistance of 50 omega through a lead 4; the porous catalytic cathode 3 in the first primary battery unit is connected with the active metal anode 1 in the second primary battery unit through an external lead 4; the porous catalytic cathode 3 in the second primary battery unit is connected with the active metal anode 1 in the third primary battery unit through an external lead 4, and so on; each galvanic cell is separated from another by a porous dielectric separator layer 2.
Secondly, the wastewater is treated by utilizing the water treatment device
1. Treating the waste water containing hexavalent chromium with the concentration of 50 mg/L
The water treatment device is used for treating the waste water containing 50 mg/L hexavalent chromium, and comprises the following steps:
the hexavalent chromium ion with the concentration of 50 mg/L is addedThe pH value of the wastewater is adjusted to 2.0, and the wastewater passes through the porous catalytic cathode along the direction of an electrode (shown by an arrow) at the flow speed of 1cm/s for 5 s; the output voltage is 1.2V, the active metal anode loses electrons and transmits the electrons to the porous catalytic cathode through an external resistor, under the action of the catalyst, hexavalent chromium obtains electrons on the surface of the porous catalytic cathode and is reduced into low-valence chromium (trivalent), the pH value of the wastewater is adjusted to 8.0, so that low-valence metal ions are coprecipitated (trivalent chromium and trivalent iron), the precipitate is removed from the wastewater, and the synchronous electricity generation and the conversion of hexavalent chromium ions can be completed. The removal rate of hexavalent chromium reaches 95 percent, and the power density of the generated electricity is 230W/m3. The electricity generation power density calculation formula is as follows: p ═ UI/V ═ 1.2V ═ 0.024A/0.000125m3＝230W/m3Where U is the output voltage, I is the current, and V is the volume of the electrode set.
2. Treating waste water containing 100 mg/L hexavalent chromium
The water treatment device is used for treating the hexavalent chromium wastewater containing 100 mg/L, and comprises the following steps:
regulating pH value of waste water containing 100 mg/L hexavalent chromium ions to 2.0, making the waste water pass through porous catalytic cathode along electrode direction (arrow head) at flow rate of 5cm/s, staying for 1s, open-circuit voltage being 1.55V, making active metal anode lose electrons and transferring the electrons to porous catalytic cathode by means of external resistor, under the action of catalyst making hexavalent chromium obtain electrons on the surface of porous catalytic cathode and reduce them into low-valence chromium (trivalent), regulating pH value of waste water to 8.0 making low-valence metal ions implement coprecipitation (trivalent chromium and trivalent iron), removing precipitate from waste water so as to implement conversion of synchronously producing electricity and hexavalent chromium ions, removing hexavalent chromium to 90%, and making electricity-producing power density be 384W/m3. The electricity generation power calculation formula is as follows: p ═ UI/V ═ 1.55V × 0.031A/0.000125m3＝384W/m3Where U is the output voltage, I is the current, and V is the volume of the electrode set.
3. Treating waste water containing 100 mg/L hexavalent chromium
The water treatment device is used for treating the hexavalent chromium wastewater containing 100 mg/L, and comprises the following steps:
will contain the concentrateRegulating pH value of waste water containing hexavalent chromium ions with a concentration of 100 mg/L to 2.0, making the waste water pass through a porous catalytic cathode along the direction of an electrode (arrow head) at a flow rate of 10cm/s for a retention time of 1s, keeping open-circuit voltage of 2.25V, making the active metal anode lose electrons and transfer the electrons to the porous catalytic cathode through an external resistor, reducing the hexavalent chromium ions on the surface of the porous catalytic cathode to low-valence chromium (trivalent) under the action of a catalyst, regulating pH value of the waste water to 8.0 to make the low-valence metal ions co-precipitate (equivalent trivalent chromium and trivalent iron), removing the precipitate from the waste water, thus completing the conversion of synchronously producing electricity and hexavalent chromium ions, wherein the removal rate of hexavalent chromium reaches 90%, and the electricity-producing power density is 810W/m3. The electricity generation power calculation formula is as follows: p ═ UI/V ═ 2.25V ×. 0.045A/0.000125m3＝810W/m3Where U is the output voltage, I is the current, and V is the volume of the electrode set.
Claims (7)
1. A water treatment device for synchronously generating electricity and converting high-valence metal ions is characterized in that: it comprises an electrochemical system; the electrochemical system comprises at least one galvanic cell; each galvanic cell comprises:
the active metal anode is made of metal with a negative standard electrode potential;
a porous catalytic cathode comprising a porous electrically conductive substrate;
the porous catalytic cathode further comprises a catalyst supported on the porous electrically conductive substrate;
the catalyst is polyaniline, polypyrrole, palladium, gold or platinum;
the loading capacity of the catalyst is 10-50 mg/cm2；
A porous dielectric separator layer separating the active metal anode and the porous catalytic cathode;
the porous dielectric isolation layer is made of polyurethane, nylon or polypropylene fiber;
the porosity of the porous catalytic cathode is 30% -90%;
the thickness of the porous catalytic cathode is 1-10 mm;
the porous conductive substrate is graphite felt, carbon cloth, carbon paper, foamed nickel, foamed copper or foamed titanium;
the porosity of the porous dielectric isolation layer is 40% -70%, and the pore diameter is 0.1-1.2 mu m;
the thickness of the porous dielectric isolation layer is 1-5 mm.
2. The water treatment apparatus according to claim 1, characterized in that: the active metal anode is made of aluminum, iron or zinc.
3. The water treatment apparatus according to claim 1 or 2, characterized in that: the connection mode of the electrodes in the electrochemical system is unipolar connection or bipolar connection;
the number of the primary battery units is 1, and the connection mode is single-pole connection;
the number of the primary battery units is more than or equal to 2, and the connection mode is repolarization connection.
4. A method for realizing synchronous electricity generation and conversion of high-valence metal ions in wastewater by using the water treatment device as claimed in any one of claims 1 to 3, comprising the following steps: and the wastewater containing high-valence metal ions passes through the porous catalytic cathode, the active metal anode loses electrons and transfers the electrons to the porous catalytic cathode through an external resistor and/or an energy storage device, and the electrons obtained by the high-valence heavy metal ions on the surface of the porous catalytic cathode are reduced into low-valence metal ions, so that the synchronous electricity generation and the conversion of the high-valence metal ions are completed.
5. The method of claim 4, wherein: the entering direction of the wastewater containing the high valence metal ions is parallel to the direction of the electrode.
6. The method according to claim 4 or 5, characterized in that: the high valence metal ions are reduced under the action of the catalyst loaded on the surface of the porous catalytic cathode.
7. The method according to claim 4 or 5, characterized in that: the method also comprises the step of coprecipitating the obtained low-valence metal ions by adjusting the pH value of the wastewater after reducing the high-valence metal ions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3383384A (en) * | 1983-10-18 | 1985-04-26 | Gnb Batteries Inc. | Membrane processess for pollution control |
| CN101967017A (en) * | 2010-11-05 | 2011-02-09 | 北京化工大学 | Electrochemical device for wastewater treatment and method for treating wastewater by using same |
| CN102340015B (en) * | 2011-07-28 | 2014-01-29 | 西安交通大学 | Microorganism electrochemical system capable of realizing electricity generation, hydrogen generation and sewage treatment simultaneously |
| CN104310573A (en) * | 2014-11-19 | 2015-01-28 | 江南大学 | Combination electrode preparation method and application of combination electrode preparation method in bioelectricity Fenton system |
| CN104787860A (en) * | 2015-04-14 | 2015-07-22 | 哈尔滨工程大学 | Method for treating hexavalent chromium in waste water by utilizing metal semi-fuel cell |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3383384A (en) * | 1983-10-18 | 1985-04-26 | Gnb Batteries Inc. | Membrane processess for pollution control |
| CN101967017A (en) * | 2010-11-05 | 2011-02-09 | 北京化工大学 | Electrochemical device for wastewater treatment and method for treating wastewater by using same |
| CN102340015B (en) * | 2011-07-28 | 2014-01-29 | 西安交通大学 | Microorganism electrochemical system capable of realizing electricity generation, hydrogen generation and sewage treatment simultaneously |
| CN104310573A (en) * | 2014-11-19 | 2015-01-28 | 江南大学 | Combination electrode preparation method and application of combination electrode preparation method in bioelectricity Fenton system |
| CN104787860A (en) * | 2015-04-14 | 2015-07-22 | 哈尔滨工程大学 | Method for treating hexavalent chromium in waste water by utilizing metal semi-fuel cell |
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