CN115159665A - Device for removing heavy metal ions in coking sludge - Google Patents

Device for removing heavy metal ions in coking sludge Download PDF

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Publication number
CN115159665A
CN115159665A CN202211101381.3A CN202211101381A CN115159665A CN 115159665 A CN115159665 A CN 115159665A CN 202211101381 A CN202211101381 A CN 202211101381A CN 115159665 A CN115159665 A CN 115159665A
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cathode
mfc
mec
anode
heavy metal
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赵煜
王霞霞
张武胜
王海成
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Taiyuan University of Technology
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/005—Combined electrochemical biological processes
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention belongs to the technical field of coking sludge treatment, and particularly relates to a device for removing heavy metal ions in coking sludge, which is a microbial fuel cell and microbial electrolysis cell combined device and contains electrolyte solution, heavy metal ions, a cation exchange membrane, a biological anode, a biological cathode and the like; directionally domesticating a biomembrane cathode resisting single heavy metal toxicity by regulating and controlling an applied voltage; organic matters are used as a carbon source and heavy metal ions in the coking sludge leaching solution are reduced through a biological cathode. The invention adopts the combination of the microbial fuel cell and the microbial electrolytic cell to treat heavy metal ions in the coking sludge leaching solution, accelerates the degradation of the heavy metal ions in the coking sludge by establishing the biological cathode, improves the biological activity of a heavy metal biochemical treatment method, and can effectively treat organic matters such as phenol and the like in the leaching solution by the principle that the microorganisms in the anode chamber oxidize the organic matters in the device.

Description

Device for removing heavy metal ions in coking sludge
Technical Field
The invention belongs to the technical field of coking sludge treatment, and particularly relates to a device for removing heavy metal ions in coking sludge.
Background
The economy develops rapidly, people live peacefully, but the ecological environment of China is more and more serious, and the damage is irreversible, thus seriously threatening the future development of human beings. At present, coking sludge generated by a traditional biochemical method used by most of domestic factories contains various organic matters and heavy metal components such as Pb, cd, cr, hg and the like, and the main treatment means of the coking sludge is a sludge coal blending coking method, so that the heavy metal content in incineration flue gas is increased, the leaching toxicity of heavy metals in incineration slag and the like have great environmental pollution and harm to human health.
The microbial electrolysis cell with biological cathode is a new pollution treatment and energy-saving technology which is developed in recent years, and the activity of the technology for treating heavy metal is obviously higher than that of the traditional biochemical method. And a biocathode based on living microbial cells (electro-nutrients) to reduce overpotential has advantages of low cost, continuous regeneration and non-corrosion, etc. compared with a non-biocathode. In early researches, the biocathode microbial electrolysis cell is mainly used for preparing hydrogen, and can be developed to perform wastewater treatment, desalination, chemical product production and the like. The performance of the cathode material influences the reduction efficiency of the whole electrolytic cell, and noble metals such as platinum meshes and the like are generally selected as the cathode of the electrolytic cell, so that the overpotential of the cathode reaction can be effectively reduced, and the overall performance of the electrolytic cell is improved. However, platinum has high cost and short service life, and many researchers have focused on alloy catalytic electrodes, carbon materials, and the like.
With the development of research, the use of microbial electrolysis cells has shown great promise in metal removal or recovery. Such as: huang et al use sodium bicarbonate as a carbon source and recover various heavy metal ions on a biological cathode in a so-called dual-chamber electrochemical system, because of low internal resistance, simple structure, high cost effectiveness, practical and convenient maintenance; single-chamber bioelectrochemistry of abouraded et al shows more advantages in treating combined organic and heavy metal wastewater; chenyizai et al studied the efficiency of the biological cathode for removing cadmium under different voltages and different carbon sources, and the organic matter as the cathode carbon source can effectively improve the concentration of cadmium removal of the device.
Disclosure of Invention
The invention aims to provide a device for removing heavy metal ions in coking sludge by a biological cathode electrochemical system, which adopts a microbial fuel cell and a microbial electrolysis cell to jointly remove the heavy metal ions and organic matters in a coking sludge leaching solution and realizes harmless full treatment of the coking sludge.
In order to achieve the purpose, the invention adopts the following technical scheme:
a device for removing heavy metal ions in coking sludge comprises a coking sludge leaching liquid tank, an MFC (Microbial fuel cell) cathode chamber, an MFC chromium removal cathode, an MFC mercury removal cathode, a common anode chamber, an MFC anode, an MEC (Microbial electrolysis cell) cathode chamber, an MEC lead removal cathode, an MEC cadmium removal cathode, a recovery tank, a liquid storage tank, a first pump and a second pump;
the outlet of the coking sludge leaching liquid tank is connected with the inlet of the MFC cathode chamber, the MFC chromium-removing cathode and the MFC mercury-removing cathode are arranged in the MFC cathode chamber, the outlet of the MFC cathode chamber is connected with the inlet of the MEC cathode chamber through a first pump, the MEC lead-removing cathode and the MEC cadmium-removing cathode are arranged in the MEC cathode chamber, the outlet of the MEC cathode chamber is connected with the inlet of the liquid storage tank, the outlet of the liquid storage tank is connected with the common anode chamber through a second pump, the outlet shared by the anode chambers is connected with the recovery tank, the MFC anode and the MEC anode are arranged in the common anode chamber, the MFC chromium-removing cathode is connected with the mercury-removing cathode in series and is connected with the MFC anode through a thin copper wire and a fixed resistance box, the MEC anode is connected with the MEC lead-removing cathode and the MEC cadmium-removing cathode through an external power supply, the MEC lead-removing cathode and the MEC cadmium-removing cathode are connected in parallel, and cation exchange membranes are arranged in the MFC cathode chamber, and the MFC cathode chamber are used for separating the corresponding anode.
Further, the external power supply is a direct-current stabilized power supply, the intermittent output voltage of the power supply is 0.3V and 0.5V, and the intermittent time is 4h; the fixed resistance box is 500 omega or 1000 omega.
Further, the MFC anode and the MEC anode are biomembrane anodes, the electrode substrate materials of the MFC anode and the MEC anode are carbon felt, carbon rods, carbon nanotubes, carbon particles, carbon brushes or graphite felt, and the MFC anode is two electrodes connected in series.
Further, the electrolyte in the common anode chamber consists of a buffer solution and a carbon source, wherein the buffer solution is disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate and sodium bicarbonate, and the carbon source is glucose, sodium acetate, sodium bicarbonate and organic matters in coking wastewater.
Further, the MFC chromium removal cathode, the MFC mercury removal cathode, the MEC lead removal cathode and the MEC cadmium removal cathode are composed of a cathode current collector and a biological cathode film loaded with microorganisms on the surface of the cathode current collector, and the cathode current collector is a stainless steel net, a platinum net, an iron net, a titanium net or foamed nickel.
Furthermore, the preparation method of the MFC chromium-removing cathode, the MFC mercury-removing cathode, the MEC lead-removing cathode and the MEC cadmium-removing cathode comprises the following steps:
(1) According to the mass ratio of 2:1, weighing graphene oxide and titanium dioxide powder, adding the graphene oxide and the titanium dioxide powder into secondary distilled water, and performing ultrasonic dispersion to obtain stable dispersion liquid;
(2) Polishing the cathode current collector by using aluminum oxide powder with the particle size of 0.05 mu m, carrying out ultrasonic cleaning by using absolute ethyl alcohol and distilled water in sequence, and drying at room temperature;
(3) Adding 0.05mol/L NaCl solution into the dispersion liquid obtained in the step (1), placing the cathode current collector obtained in the step (2) into the dispersion liquid, introducing nitrogen to drive oxygen, and depositing graphene oxide and titanium dioxide on the cathode current collector by adopting a cyclic voltammetry method;
(4) Under the condition of external voltage, domesticating the cathode current collector obtained in the step (3) in an electrolyte solution containing electrogenic flora and a carbon source through electrode polarity reversal to obtain a corresponding biological cathode;
(5) Starting the biological cathode by adopting a gradient domestication mode, namely gradually increasing the concentration of four heavy ions in the simulated electrolyte in a range of 5-20mg/L until a stable heavy metal removal rate is obtained in a plurality of batches, so as to obtain a biological membrane cathode resisting single heavy metal toxicity;
(6) And sequentially enabling the mixed solution of 3.0mg/L of Cr (VI), 1.0mg/L of Hg (II), 3.0mg/L of Cd (II) and 1.0mg/L of Pb (II) to flow through the MFC cathode chamber and the MEC cathode chamber, and increasing the concentration of various metal ions to 5mg/L after multiple cycles to obtain the MFC chromium removal cathode, the MFC mercury removal cathode, the MEC lead removal cathode and the MEC cadmium removal cathode.
Compared with the prior art, the invention has the following advantages:
1. the device adopts a biological cathode type microbial fuel cell and microbial electrolysis cell combined system to effectively remove four heavy metal ions in the coking sludge leaching solution, and synchronously realizes the removal of organic matters in the sludge leaching solution by utilizing the mechanism that an anode decomposes the organic matters to provide electrons.
2. The cathode of the device uses the deposition of carbon materials and metal materials in nano materials in a stainless steel mesh, a platinum mesh, an iron mesh, a titanium mesh and foam nickel, so that the surface area and the conductivity of the cathode electrode are improved, and the device has good adaptability and good treatment effect on the coking sludge leaching solution, and has efficient and stable performance.
3. The anode of the microbial fuel cell and the anode of the microbial electrolytic cell are arranged in a common anode chamber, so that the construction cost of the device is greatly reduced, and the real continuous operation is realized.
4. The microbial electrolysis cell of the device adopts an intermittent operation mode, so that the heavy metal is effectively removed, and the device has simple process and convenient operation.
Drawings
FIG. 1 is a schematic view of an apparatus for removing heavy metal ions from a coked sludge;
the system comprises a 1-coking sludge leaching liquid tank, a 2-MFC chromium removal cathode, a 3-MFC cathode chamber, a 4-MFC mercury removal cathode, a 5-MFC anode, a 6-shared anode chamber, a 7-MEC anode, an 8-external power supply, a 9-MEC cathode chamber, a 10-MEC lead removal cathode, an 11-MEC cadmium removal cathode, a 12-recovery tank, a 13-liquid storage tank, a 14-first pump and a 15-second pump, wherein the coking sludge leaching liquid tank is connected with the 1-MFC cathode chamber;
FIG. 2 is a diagram of heavy metal ion removal under open and closed circuit conditions by a device for removing heavy metal ions from coked sludge;
FIG. 3 is a LSV graph of four heavy metal ions;
FIG. 4 is an EIS diagram of four heavy metal ions;
FIG. 5 is a plot of polarization curve and power density at 5mg/L of chromium and mercury in MFC.
Detailed Description
Example 1
As shown in fig. 1, the device for removing heavy metal ions in the coking sludge comprises a coking sludge leaching liquid tank 1, an MFC cathode chamber 3, an MFC chromium removal cathode 2, an MFC mercury removal cathode 4, a common anode chamber 6, an MFC anode 5, an MEC anode 7, an MEC cathode chamber 9, an MEC lead removal cathode 10, an MEC cadmium removal cathode 11, a recovery tank 12, a liquid storage tank 13, a first pump 14 and a second pump 15;
the outlet of the coking sludge leaching liquid tank 1 is connected with the inlet of an MFC cathode chamber 3, the MFC chromium-removing cathode 2 and the MFC mercury-removing cathode 4 are arranged on the MFC cathode chamber 3, the outlet of the MFC cathode chamber 3 is connected with the inlet of an MEC cathode chamber 9 through a first pump 14, the MEC lead-removing cathode 10 and the MEC cadmium-removing cathode 11 are arranged on the MEC cathode chamber 9, the outlet of the MEC cathode chamber 9 is connected with the inlet of a liquid storage tank 13, the outlet of the liquid storage tank 13 is connected with a common anode chamber 6 through a second pump 15, the outlet of the common anode chamber 6 is connected with a recovery tank 12, the MFC anode 5 and the MEC anode 7 are arranged on the common anode chamber 6, the MFC chromium-removing cathode 2 is connected with the MFC mercury-removing cathode 4 in series and connected with the MFC anode 5 through a thin copper wire and a fixed resistance box, the MEC anode 7 is connected with the MEC lead-removing cathode 10 and the MEC cadmium-removing cathode 11 through an external power supply 8, the MEC lead-removing cathode 10 and the MEC cadmium-removing cathode 11 are connected in parallel, and cation exchange membranes are arranged in the MFC cathode chamber 3, the common anode chamber 6 and the MEC cathode chamber 9 respectively.
Wherein, the external power supply 8 is a direct current stabilized power supply, the intermittent output voltage of the power supply is 0.3V and 0.5V, and the intermittent time is 4h; the fixed resistance box is 500 omega or 1000 omega.
The MFC anode 5 and the MEC anode 7 are biomembrane anodes, the electrode substrate materials of the MFC anode 5 and the MEC anode 7 are carbon felts, and the MFC anode 5 is two electrodes connected in series.
The preparation method of the biomembrane anode comprises the following specific steps:
(1) Pretreating the MFC anode and the MEC anode: washing with deionized water; soaking in 0.5mol/L hydrochloric acid solution for 2h; soaking in 0.5mol/L sodium hydroxide solution for 2h; washing with deionized water again until the pH value is 6.8 to 7.5; drying at 100 deg.C.
(2) Activating the aerobic bacterial sludge and the anaerobic bacterial sludge and mixing the activated aerobic bacterial sludge and the anaerobic bacterial sludge in a mass ratio of 1;
(3) Domesticating in a single-chamber microbial electrolytic cell with the applied voltage of 1.5-2.0V, a buffer solution and a carbon source, wherein the pH of the electrolyte is 6.5-7.5;
(4) And recording the output current, and when the output maximum current reaches the maximum value and is stably output, namely the biological membrane acclimation is completed.
The electrolyte in the common anode chamber 6 consists of a buffer solution and a carbon source, wherein the buffer solution is disodium hydrogen phosphate, and the carbon source is glucose.
The MFC chromium removal cathode 2, the MFC mercury removal cathode 4, the MEC lead removal cathode 10 and the MEC cadmium removal cathode 11 are composed of a cathode current collector and a biological cathode film which loads microorganisms on the surface of the cathode current collector, and the cathode current collector is a stainless steel net.
The preparation method of the MFC chromium-removing cathode 2, the MFC mercury-removing cathode 4, the MEC lead-removing cathode 10 and the MEC cadmium-removing cathode 11 comprises the following steps:
(1) According to the mass ratio of 2:1, weighing graphene oxide and titanium dioxide powder, adding the graphene oxide and the titanium dioxide powder into secondary distilled water, and performing ultrasonic dispersion to obtain stable dispersion liquid;
(2) Polishing the cathode current collector by using aluminum oxide powder with the particle size of 0.05 mu m, sequentially performing ultrasonic cleaning by using absolute ethyl alcohol and distilled water, and drying at room temperature;
(3) Adding 0.05mol/L NaCl solution into the dispersion liquid obtained in the step (1), placing the cathode current collector obtained in the step (2) into the dispersion liquid, introducing nitrogen to drive oxygen, and depositing graphene oxide and titanium dioxide on the cathode current collector by adopting a cyclic voltammetry method;
(4) Under the condition of an external voltage of 1.5V, domesticating the cathode current collector obtained in the step (3) in an electrolyte solution containing an electrogenic flora and a carbon source through electrode polarity reversal to obtain a corresponding biological cathode;
(5) Starting the biological cathode by adopting a gradient domestication mode, namely gradually increasing the concentration of four heavy ions in the simulated electrolyte in a range of 5-20mg/L until a stable heavy metal removal rate is obtained in a plurality of batches, so as to obtain a biological membrane cathode resisting single heavy metal toxicity;
(6) And sequentially enabling the mixed solution of 3.0mg/L Cr (VI), 1.0mg/L Hg (II), 3.0mg/L Cd (II) and 1.0mg/L Pb (II) to flow through the MFC cathode chamber 3 and the MEC cathode chamber 9, and increasing the concentration of various metal ions to 5mg/L after multiple cycles to obtain the MFC chromium removal cathode 2, the MFC mercury removal cathode 4, the MEC lead removal cathode 10 and the MEC cadmium removal cathode 11.
Example 2
The device for treating coking wastewater and producing hydrogen synchronously in the embodiment is the same as that in the embodiment 1, the anode is the domesticated biological carbon felt in the embodiment 1, and the cathode is the cathode biological membrane electrode in the embodiment 1. Assembling electrodes into the device, and selecting 500 Ω as external resistance of microbial fuel cell and 4h as external voltage intermittent time of microbial electrolytic cell, and buffer solution (NaH) 2 PO 4 ·2H 2 O 3.32g/L、Na 2 HPO 4 ·12H 2 O10.32 g/L,) and nutrient solution (CH) 3 COONa·3H 2 O 1g/L、NH 4 Cl 0.31g/L、KCI 0.13mg/L、CaC1 2 0.01g/L、MgSO 4 1.2g/L、NaCl 11.36g/L、FeSO 4 6mg/L、MnSO 4 0.76mg/L、AIC1 3 0.5mg/L、NiC1 2 ·6H 2 O 0.1mg/L、CuC1 2 0.53816mg/L、ZnC1 2 1mg/L、CoC1 2 ·2H 2 O1 mg/L) according to a weight ratio of 10:2 (V/V) is continuously pumped into the common anode compartment and the char sludge leachate is continuously pumped into the MFC cathode compartment and high purity nitrogen is purged into the MFC cathode compartment and the MFC cathode compartment to drive out dissolved oxygen in the cathode compartment solution. Organic matters in the anode chamber are shared, electrons and protons are released, the electrons in the MFC cathode chamber are transferred into the cathode chamber through an external circuit, the protons reach the MFC cathode chamber through a cation exchange membrane, the cathode electrode receives the electrons and the protons to reduce chromium ions and mercury ions, the electrons in the MEC cathode chamber are transferred into the cathode chamber through the external circuit under the action of a potential difference provided by an external voltage, and the protons are transferred into the cathode chamber through the cation exchange membraneThe membrane reaches the cathode compartment. Then, carrying out reduction of cadmium ions and lead ions on a biomembrane cathode in the MEC cathode chamber; finally, the treated coking wastewater flows into a liquid storage tank for oxidation treatment of organic matters; detecting the concentration of various heavy metal ions in the effluent, and entering a recovery tank if the concentration reaches the discharge standard; if the detection is not qualified, the device is re-entered for continuous processing.
Fig. 2 is a comparison of the removal rates of heavy metals in closed circuit condition and open circuit condition, and it can be seen from the graph that the removal rates of chromium ions, mercury ions, cadmium ions, and lead ions, which are heavy metals having a concentration of 5mg/L in the closed circuit condition, are 89%, 93%, 92%, and 95%, while the removal rates in the open circuit condition are only 13%, 17%, 14%, and 19%. Only the bioadsorption effect exists in the open circuit state, and the removal of heavy metals in the presence of current is proved to be the bioelectrochemical effect.
Fig. 3 is a linear scanning voltammogram of four heavy metal ions, from which it can be seen that the mercury ion curve has a larger current response than the other three heavy metal ions, which indicates that the electron transfer rate is faster, and that the electrochemical active substance existing on the electrode promotes the redox reaction, which also reflects that the cathode electrode acclimation in the method obtains a higher microbial density, greatly shortens the time for acclimating the cathode, and improves the efficiency of the device.
Fig. 4 is an impedance spectrogram of four heavy metal ions, which is composed of a relatively large semicircular part and a relatively small linear part, and shows that the electrochemical reaction on the biological membrane is a slow electron transfer process, and the difference between the ohmic impedance and the diffusion impedance of various solutions is not large. The ohmic resistances of chromium ions, mercury ions, cadmium ions and lead ions are 6.2 Ω, 3.6 Ω, 6.1 Ω and 4.0 Ω, and the charge transfer resistances thereof are 13.359 Ω, 20.91 Ω, 8.4551 Ω and 7.0535 Ω. Indicating that the electrochemical performance of mercury ions is the best because an electrode with low ohmic resistance can obtain effective conductivity and accelerate the transfer of electrons.
FIG. 5 is a power density diagram and a polarization curve diagram of the removal of chromium ions and mercury ions by a microbial fuel cell, and it can be seen that the maximum power of 5mg/L of chromium ions and mercury ionsThe density is 9.11mW/m 2 、10.23 mW/m 2 And a maximum current density of 149mA/m 2 、201 mA/m 2 . The power density diagram and the polarization curve diagram prove that the microbial fuel cell does not need external energy input, can generate certain electric energy and has certain advantages.
Example 3
A method for acclimating a cathode biofilm electrode by using the device, comprising the following steps:
(1) Activated coking wastewater bacteria
Mixing aerobic bacterial sludge and anaerobic bacterial sludge of a coking plant in a ratio of 1:1, and performing activation culture in a constant-temperature shaking box at the temperature of 35 ℃ for 3 days;
the nutrient solution comprises the following components: CH (CH) 3 COONa·3H 2 O 1g/L、NH 4 Cl 0.31g/L、KCl 0.13mg/L、CaC1 2 0.01g/L、MgSO 4 1.2g/L、NaCl 11.36g/L、FeSO 4 6mg/L、MnSO 4 0.76mg/L、AIC1 3 0.5mg/L、NiC1 2 ·6H 2 O 0.1mg/L、CuC1 2 0.53816mg/L、ZnC1 2 1mg/L、CoC1 2 ·2H 2 O1 mg/L; the preparation method of the microbial buffer solution comprises the following steps: naH (sodium hydroxide) 2 PO 4 ·2H 2 O 3.32g/L、Na 2 HPO 4 ·12H 2 O10.32 g/L, and adjusting the pH value of the mixed solution to 6.8-7.2 by using HCI and NaOH solutions.
(2) Pretreatment of MFC anodes and MEC anodes
Firstly, washing by using distilled water; then soaking in 0.5 mol/HCI for 2 hours and 0.5mol/LNaOH for 2 hours respectively, finally soaking in distilled water for 5 hours, flushing until the pH value is 6.8 to 7.2, and drying at 120 ℃ for 12 hours.
(3) Acclimatization of anodic biofilms
Adding 20% of mixed bacteria source of aerobic bacteria and anaerobic bacteria, 80% of phosphoric acid buffer solution and nutrient solution into a single-chamber microbial electrolytic cell, applying voltage of 1.5-2.0V, and connecting a universal meter to monitor the output current of the electrolytic cell; and recording the current every 0.5h until the output current reaches more than 1mA to the maximum value of stability, which indicates that the anode of the carbon felt for degrading the sodium acetate biomembrane is domesticated to be mature.
(4) Preparation and domestication of cathode biomembrane electrode
Firstly, according to the mass ratio of 2:1, weighing graphene oxide and titanium dioxide powder, adding the graphene oxide and the titanium dioxide powder into secondary distilled water, and performing ultrasonic dispersion to obtain stable dispersion liquid; polishing the cathode current collector by using aluminum oxide powder with the particle size of 0.05 mu m, sequentially performing ultrasonic cleaning by using absolute ethyl alcohol and distilled water, and drying at room temperature; adding 0.05mol/L NaCl solution into the dispersion liquid obtained in the step (1), placing the cathode current collector obtained in the step (2) into the dispersion liquid, introducing nitrogen to drive oxygen, and depositing graphene oxide and titanium dioxide on the cathode current collector by adopting a cyclic voltammetry method; under the condition of external voltage, domesticating the cathode current collector obtained in the step (3) in an electrolyte solution containing electrogenic flora and a carbon source through electrode polarity reversal to obtain a corresponding biological cathode; starting the biological cathode by adopting a gradient domestication mode, namely gradually increasing the concentration of four heavy ions in the simulated electrolyte in a range of 5-20mg/L until a stable heavy metal removal rate is obtained in a plurality of batches, so as to obtain a biological membrane cathode resisting single heavy metal toxicity; and (3) sequentially enabling a mixed solution of a potassium dichromate solution of 3.0mg/L, a mercury chloride solution of 1.0mg/L, a cadmium chloride solution or a cadmium sulfate solution of 3.0mg/L and a lead nitrate solution of 1.0mg/L to flow through the MFC cathode chamber and the MEC cathode chamber, and increasing the concentration of various metals to 5mg/L after multiple cycles to obtain the cathode biomembrane electrode.

Claims (6)

1. A device for removing heavy metal ions in coking sludge is characterized by comprising a coking sludge leaching liquid tank, an MFC cathode chamber, an MFC chromium removal cathode, an MFC mercury removal cathode, a common anode chamber, an MFC anode, an MEC cathode chamber, an MEC lead removal cathode, an MEC cadmium removal cathode, a recovery tank, a liquid storage tank, a first pump and a second pump;
the outlet of the coking sludge leaching liquid tank is connected with the inlet of the MFC cathode chamber, the MFC chromium-removing cathode and the MFC mercury-removing cathode are arranged in the MFC cathode chamber, the outlet of the MFC cathode chamber is connected with the inlet of the MEC cathode chamber through a first pump, the MEC lead-removing cathode and the MEC cadmium-removing cathode are arranged in the MEC cathode chamber, the outlet of the MEC cathode chamber is connected with the inlet of the liquid storage tank, the outlet of the liquid storage tank is connected with the common anode chamber through a second pump, the outlet shared by the anode chambers is connected with the recovery tank, the MFC anode and the MEC anode are arranged in the common anode chamber, the MFC chromium-removing cathode is connected with the mercury-removing cathode in series and is connected with the MFC anode through a thin copper wire and a fixed resistance box, the MEC anode is connected with the MEC lead-removing cathode and the MEC cadmium-removing cathode through an external power supply, the MEC lead-removing cathode and the MEC cadmium-removing cathode are connected in parallel, and cation exchange membranes are arranged in the MFC cathode chamber, and the MFC cathode chamber are used for separating the corresponding anode.
2. The device for removing heavy metal ions in the coked sludge according to claim 1, wherein the external power supply is a direct-current stabilized power supply, the intermittent output voltage of the power supply is 0.3V and 0.5V, and the intermittent time is 4h; the fixed resistance box is 500 omega or 1000 omega.
3. The device for removing heavy metal ions from coked sludge according to claim 1, wherein the MFC anode and the MEC anode are biomembrane anodes, the electrode base material of the MFC anode and the MEC anode is carbon felt, carbon rods, carbon nanotubes, carbon particles, carbon brushes or graphite felt, and the MFC anode is two electrodes connected in series.
4. The device for removing heavy metal ions in coking sludge according to claim 1, wherein the electrolyte in the common anode chamber consists of a buffer solution and a carbon source, the buffer solution is disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium carbonate and sodium bicarbonate, and the carbon source is glucose, sodium acetate, sodium bicarbonate and organic matters in coking wastewater.
5. The device for removing heavy metal ions in coked sludge according to claim 1, characterized in that the MFC chromium removal cathode, the MFC mercury removal cathode, the MEC lead removal cathode and the MEC cadmium removal cathode are composed of a cathode current collector and a biological cathode film loaded with microorganisms on the surface of the cathode current collector, and the cathode current collector is a stainless steel net, a platinum net, an iron net, a titanium net or foamed nickel.
6. The device for removing heavy metal ions in the coked sludge according to claim 5, wherein the preparation method of the MFC chromium removal cathode, the MFC mercury removal cathode, the MEC lead removal cathode and the MEC cadmium removal cathode comprises the following steps:
(1) According to the mass ratio of 2:1, weighing graphene oxide and titanium dioxide powder, adding the graphene oxide and the titanium dioxide powder into secondary distilled water, and performing ultrasonic dispersion to obtain stable dispersion liquid;
(2) Polishing the cathode current collector by using aluminum oxide powder with the particle size of 0.05 mu m, carrying out ultrasonic cleaning by using absolute ethyl alcohol and distilled water in sequence, and drying at room temperature;
(3) Adding 0.05mol/L NaCl solution into the dispersion liquid obtained in the step (1), placing the cathode current collector obtained in the step (2) into the dispersion liquid, introducing nitrogen to drive oxygen, and depositing graphene oxide and titanium dioxide on the cathode current collector by adopting a cyclic voltammetry method;
(4) Under the condition of external voltage, domesticating the cathode current collector obtained in the step (3) in an electrolyte solution containing an electrogenic flora and a carbon source through electrode polarity reversal to obtain a corresponding biological cathode;
(5) Starting the biological cathode by adopting a gradient domestication mode, namely simulating the concentration of four heavy ions in the electrolyte to gradually increase from 5 to 20mg/L until a stable heavy metal removal rate is obtained in a plurality of batches, so as to obtain a biological membrane cathode resisting single heavy metal toxicity;
(6) And sequentially enabling the mixed solution of 3.0mg/L Cr (VI), 1.0mg/L Hg (II), 3.0mg/L Cd (II) and 1.0mg/L Pb (II) to flow through the MFC cathode chamber and the MEC cathode chamber, and increasing the concentration of various metal ions to 5mg/L after multiple cycles to obtain the MFC chromium-removing cathode, the MFC mercury-removing cathode, the MEC lead-removing cathode and the MEC cadmium-removing cathode.
CN202211101381.3A 2022-09-09 2022-09-09 Device for removing heavy metal ions in coking sludge Pending CN115159665A (en)

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