CN107311294B - Device and method for simultaneously treating park sludge and electroplating wastewater in electroplating industrial park - Google Patents

Device and method for simultaneously treating park sludge and electroplating wastewater in electroplating industrial park Download PDF

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CN107311294B
CN107311294B CN201710727172.2A CN201710727172A CN107311294B CN 107311294 B CN107311294 B CN 107311294B CN 201710727172 A CN201710727172 A CN 201710727172A CN 107311294 B CN107311294 B CN 107311294B
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chamber
sludge
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CN107311294A (en
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赵庆良
于航
梁柱元
董全胜
姜珺秋
王琨
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Harbin Institute 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
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/006—Electrochemical treatment, e.g. electro-oxidation or electro-osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/02—Biological treatment
    • 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
    • C02F3/30—Aerobic and anaerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
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    • C02F2101/20—Heavy metals or heavy metal compounds
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
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    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/20—Sludge processing

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Abstract

A device and a method for simultaneously treating sludge and electroplating wastewater in an electroplating industrial park relate to a device and a method for treating sludge and wastewater and aim to solve the technical problems of slow degradation rate, poor operation stability and poor continuity of the conventional double-chamber fuel cell electroplating wastewater reduction technology. The device comprises a biological cathode chamber, an anode chamber, a chemical cathode chamber, an external accumulator and a proton exchange membrane; each chamber is separated by a proton exchange membrane, each chamber is provided with a graphite brush electrode, and functional bacteria are attached to each electrode except the chemical cathode chamber; the biological cathode chamber is connected with the electrodes in the chemical cathode chamber in parallel, and then is connected with the graphite brush electrode in the anode chamber through an external accumulator to form a closed loop. The treatment method comprises the following steps: adding nutrient solution into the biological cathode chamber, adding sludge into the anode chamber, adding electroplating wastewater into the chemical cathode chamber, and replacing the substrate on time to complete the treatment of the sludge and the electroplating wastewater. Is suitable for treating wastewater and sludge containing chromium, nickel, copper, zinc, cadmium and other ions.

Description

Device and method for simultaneously treating park sludge and electroplating wastewater in electroplating industrial park
Technical Field
The invention relates to a device and a method for treating sludge and electroplating wastewater, belongs to the field of bioelectrochemistry, and particularly relates to a method for realizing reclamation and stabilization of sludge in an electroplating industrial park, and reducing heavy metal ions in the electroplating wastewater and synchronously generating electricity.
Background
The electroplating industry in China is lack of reasonable layout for a long time, the enterprise market and technical management work in the industry is weak, the production technology is backward, the information is closed, the overall level of the industry is not high, the overall composition of an enterprise is unreasonable, the development level in the industry is uneven, the number of enterprises is large, the scale is small, the points are wide, the operation is dispersed, and the pollutant generation amount is large. In the running process of an electroplating factory in an electroplating industrial park, electroplating solution filtration, plated part cleaning, factory cleaning and the like enable electroplating wastewater containing heavy metal ions to enter a drainage pipeline. The waste water comes from various bath solutions and water which are leaked, emitted, dripped and leaked due to the leakage of plating pretreatment, plating layer rinsing, post-treatment, workshop scouring and plating bath leakage or improper operation management, and the main heavy metals contained in the waste water comprise chromium, cadmium, lead, copper, nickel and zinc. If discharged into the environment, heavy metal ions can cause wider and more serious harm to human beings through the enrichment effect of drinking water and food chains.
Wastewater is classified according to the type of electroplating, and generally classified into chromium-containing wastewater, nickel-containing wastewater, copper-containing wastewater, zinc-containing wastewater, cadmium-containing wastewater and the like. The heavy metals contained in the wastewater from electroplating plants are mainly chromium, depending on the processed articles and the quantity. The most common methods for treating heavy metal wastewater in the electroplating industrial park are a chemical reduction method, an electrolysis method and a membrane method. The chemical reduction method adds a large amount of chemical agents, so that the continuous investment amount is large, and secondary pollution is caused by the added agents. The electrolysis method has high electricity consumption, and the method is not economical and effective. The membrane method consumes much energy and is easy to cause the problems of membrane pollution and the like. The construction of the double-chamber microbial fuel cell can accelerate the degradation of organic matters in sludge and simultaneously realize the reduction of heavy metal ions of the cathode, and the treatment of electroplating wastewater by using the microbial fuel cell becomes a hotspot of research at present. Chinese patent publication No. CN104386826A discloses a method for treating and monitoring chromium-containing wastewater based on a microbial fuel cell. The reactor takes anaerobic sludge and sodium acetate solution as matrixes in an anode, and catholyte is added into a cathodeAnd (5) starting. After the voltage is stabilized, the anode is replaced by oxygen-free anolyte, and the cathode is electroplating wastewater containing chromium. The method has long period, and the anode and the cathode simultaneously change the matrix during formal operation, the disturbance is large, and the operation stability is poor; in addition, the method is influenced by the decrease of the chromium concentration during the operation, the electron accumulation and the activity of the anode electrogenesis bacteria are reduced, and the time for recovering the activity is long. Water treatment technology, 39 vol.11, 2013, published in volume 39, and published in volume 11, microbial Fuel cell purification of Cu-containing2+Wastewater resource treatment research, the first article proposes a double-chamber MFC model for reducing Cu in wastewater2+. But also has the problems of poor operation stability, great influence on anode electrogenesis bacteria after the concentration of the heavy metal ions is reduced, and reduction rate reduction of the heavy metal ions.
Disclosure of Invention
The invention aims to solve the technical problems of slow degradation rate, poor operation stability and poor continuity of the existing dual-chamber fuel cell reduction technology for electroplating wastewater, and provides a device and a method for simultaneously treating park sludge and electroplating wastewater in an electroplating industrial park.
The device for simultaneously treating the sludge and the electroplating wastewater in the electroplating industrial park comprises a biological cathode chamber 1, an anode chamber 2, a chemical cathode chamber 3, an external accumulator or an electric appliance 4 and a proton exchange membrane 5;
wherein the anode chamber 2 is positioned between the biological cathode chamber 1 and the chemical cathode chamber 3, and the biological cathode chamber 1 and the anode chamber 2 and the chemical cathode chamber 3 are separated by proton exchange membranes 5;
a first graphite brush electrode 1-1 and an aeration device 1-2 are arranged in the biological cathode chamber 1, carbon granules 1-3 are filled in the biological cathode chamber 1, a first water outlet hole 1-4 is formed in the bottom of the side wall of the biological cathode chamber 1, and a first air hole 1-5 is formed in the top of the biological cathode chamber 1; aeration biological catalytic active bacteria are attached to the first graphite brush electrode 1-1 and the carbon particles 1-3;
a second graphite brush electrode 2-1 and a reference electrode 2-2 are arranged in the anode chamber 2, a second water outlet hole 2-3 is arranged at the bottom of the side wall of the anode chamber 2, and a second air hole 2-4 is arranged at the top of the anode chamber 2; electrochemical active bacteria are attached to the second graphite brush electrode 2-1;
a third graphite brush electrode 3-1 is arranged in the chemical cathode chamber 3, and no bacteria are attached to the third graphite brush electrode 3-1; a third water outlet hole 3-2 is formed in the bottom of the side wall of the chemical cathode chamber 3, and a third air hole 3-3 is formed in the top of the chemical cathode chamber 3;
the first graphite brush electrode 1-1 in the biological cathode chamber 1 and the third graphite brush electrode 3-1 in the chemical cathode chamber 3 are connected by a lead and then connected with the second graphite brush electrode 2-1 in the anode chamber 2 through an external accumulator or an electrical appliance 4 to form a closed loop.
The method for simultaneously treating the sludge and the electroplating wastewater in the electroplating industrial park by using the device comprises the following steps:
firstly, nutrient solution is added into a biological cathode chamber 1 as biological cathode electrolyte, sludge of a sewage treatment plant in an electroplating industrial park is added into an anode chamber 2 as an anode substrate, then a second air hole 2-4 is sealed, and electroplating wastewater is added into a chemical cathode chamber 3 as chemical cathode electrolyte;
and secondly, keeping the temperature of the biological cathode chamber 1, the anode chamber 2 and the chemical cathode chamber 3 at 20-40 ℃, starting the aeration device 1-2 in the biological cathode chamber 1, performing treatment, changing half of nutrient solution and electroplating wastewater every 2-5 days, and changing sludge every 5-10 days to finish the treatment of the sludge and the electroplating wastewater in the electroplating industrial park.
According to the device for simultaneously treating the sludge and the electroplating wastewater in the electroplating industrial park, the anode chamber and the two cathode chambers are separated by the proton exchange membrane, and the structure is favorable for quickly transmitting protons in the anode chamber to the cathode chambers on the two sides; the anode chamber is closed and anaerobic, anaerobic sludge containing various organic matters forms simple soluble organic matters through a hydrolysis acidification process under the anaerobic condition, the simple organic matters are utilized by electrochemical active bacteria attached to the second graphite brush electrode 2-1, and electrons generated in the metabolic process are conducted to the third graphite brush electrode 3-1 in the chemical cathode chamber and the first graphite brush electrode 1-1 in the biological cathode chamber through electrodes; electrons are utilized by chemical catholyte 3-2 in the electrochemical electrode chamber to participate in chemical reaction and react with protons and metal ionsCarrying out a bioreduction reaction; electrons are utilized by the aerated biological catalytic active bacteria in the biological cathode chamber and H+Reacts with oxygen to produce water. The graphite brush electrodes of the biological cathode chamber 1 and the chemical cathode chamber 3 are connected with the anode graphite brush through a power accumulator or an electric appliance 4, so that the generated electric energy is utilized; the chemical cathode connected with the anode has the function of reducing metal ions in the electroplating wastewater, and the biological cathode connected with the anode has the functions of stabilizing anode electrochemical active bacteria and improving reaction rate.
The invention provides a method for simultaneously treating park sludge and electroplating wastewater in an electroplating industrial park. Adopt the surplus sludge of sewage treatment plant production in the garden as the anode substrate, electroplating effluent is as chemical cathode electrolyte, and the nutrient solution is as biological cathode electrolyte, constructs novel biological electrochemical system, realizes garden sludge and electroplating effluent treatment and produces the electric energy, guarantees the electric energy output of the great degree of battery and the high-efficient processing of electroplating effluent and the electrogenesis stability of battery, and the electric energy can be applied to the biological negative pole of aeration of another device. The invention has reduction removal effect on chromium, nickel, copper, zinc, cadmium and other ions.
The invention has the advantages that ① in the starting stage of the reactor, because the activity of the aeration biological catalytic active bacteria is strong, the metabolism is rapid, and both sides adopt the aeration biological cathode for starting, the microorganism pair H+The stimulation to the electrochemical active bacteria in the anode sludge is increased due to the large demand of electrons, the generation propagation speed of the electrochemical active bacteria is accelerated, the activity of the anode electrochemical active bacteria is enhanced, the quantity of the anode electrochemical active bacteria is increased, the interspecies advantages of the anode electrochemical active bacteria are enlarged, and the starting process is accelerated, ② the cathode chamber of the aerobic organism has stronger stability and anti-interference capability compared with the anaerobic anode chamber, so that the anti-interference capability of the whole reactor is improved, ③ in the operation stage of the reactor, the concentration of heavy metal ions in the chemical cathode chamber is gradually reduced, the demand for electrons is reduced, the electrons and protons generated in the anode chamber begin to accumulate and inhibit the activity of the electrochemical active bacteria, and the existence of the biological cathode enables the electron transport of the anode to be stable and not influenced by the slowing down of the chemical cathode reaction and the reduction of the electron demandA and H+. Sufficient electrons and H +④ after ensuring a sufficiently large contact area and a certain hydraulic retention time, the reactor can completely realize continuous flow, and continuously treat electroplating wastewater containing heavy metal ions under the condition of the optimal reduction rate in the optimal operation state. ⑤ heavy metal electroplating wastewater can be degraded no matter the concentration (medium concentration, high concentration or ultrahigh concentration) is no matter whether the conditions are aerobic or anaerobic, and no matter the purity (whether other metal ions interfere with the purity) is different from the common biological treatment, and the high concentration heavy metal ions can not reduce the degradation effect of the reactor, but can accelerate the degradation rate to a certain extent. ⑥ the invention can accelerate the degradation rate of Cr ions in the chemical cathode chamber under the condition of low metal ion concentration6+Reduction to Cr3+，Cu2+Reduction to Cu2O，Ni2+Reduction to Ni, Zn2+Reduction to Zn, Cd2+Reducing the Cd into Cd. But since the redox potentials of Ni, Zn and Cd are negative (Ni)2+/Ni0SHE is-0.230V; zn2+/Zn0SHE is-0.763V; cd [ Cd ]2+/Cd0⑦, the method of the invention can efficiently reduce the heavy metals in the electroplating wastewater to facilitate the recovery of the heavy metals, and compared with the traditional treatment method of the electroplating wastewater in the electroplating industrial park, the method can also reduce the sludge amount generated in the pretreatment process before the biological treatment stage, thereby reducing the treatment cost of dangerous waste.
Drawings
FIG. 1 is a schematic view showing the construction of an apparatus for treating both sludge and electroplating wastewater of a park for electroplating industry according to the present invention; wherein 1 is a biological cathode chamber, 1-1 is a first graphite brush electrode, 1-2 is an aeration device, 1-3 is carbon particles, 1-4 is a first water outlet, and 1-5 is a first air outlet; 2 is an anode chamber, 2-1 is a second graphite brush electrode, 2-2 is a reference electrode; 2-3 is a second water outlet hole, and 2-4 is a second air outlet hole; 3 is a chemical cathode chamber, and 3-1 is a third graphite brush electrode; 3-2 is a third water outlet hole, and 3-3 is a third air outlet hole; 4 is a power storage device or an electric appliance, and 5 is a proton exchange membrane.
Detailed Description
The first embodiment is as follows: the device for simultaneously treating the sludge and the electroplating wastewater in the electroplating industrial park comprises a biological cathode chamber 1, an anode chamber 2, a chemical cathode chamber 3, an external accumulator or an electric appliance 4 and a proton exchange membrane 5; wherein the anode chamber 2 is positioned between the biological cathode chamber 1 and the chemical cathode chamber 3, and the biological cathode chamber 1 and the anode chamber 2 and the chemical cathode chamber 3 are separated by proton exchange membranes 5; a first graphite brush electrode 1-1 and an aeration device 1-2 are arranged in the biological cathode chamber 1, carbon granules 1-3 are filled in the biological cathode chamber 1, a first water outlet hole 1-4 is formed in the bottom of the side wall of the biological cathode chamber 1, and a first air hole 1-5 is formed in the top of the biological cathode chamber 1; aeration biological catalytic active bacteria are attached to the first graphite brush electrode 1-1 and the carbon particles 1-3; a second graphite brush electrode 2-1 and a reference electrode 2-2 are arranged in the anode chamber 2, a second water outlet hole 2-3 is arranged at the bottom of the side wall of the anode chamber 2, and a second air hole 2-4 is arranged at the top of the anode chamber 2; electrochemical active bacteria are attached to the second graphite brush electrode 2-1; a third graphite brush electrode 3-1 is arranged in the chemical cathode chamber 3, and biological catalytic active bacteria are aerated on the third graphite brush electrode 3-1; a third water outlet hole 3-2 is formed in the bottom of the side wall of the chemical cathode chamber 3, and a third air hole 3-3 is formed in the top of the chemical cathode chamber 3; the first graphite brush electrode 1-1 in the biological cathode chamber 1 and the third graphite brush electrode 3-1 in the chemical cathode chamber 3 are connected by a lead and then connected with the second graphite brush electrode 2-1 in the anode chamber 2 through an external accumulator or an electrical appliance 4 to form a closed loop.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the biological cathode chamber 1 is a cuboid or a cylinder; the chemical cathode chamber 3 is a cuboid or a cylinder; the rest is the same as the first embodiment.
The rectangular polar chambers have regular structure and simple preparation, and are convenient to be arranged regularly in groups according to batches; the cylindrical polar chamber has the advantages that the dead zone range generated at the corners of the polar chamber can be reduced, and the liquid concentration in the polar chamber is uniform.
The third concrete implementation mode: the difference between the first embodiment and the second embodiment is that magnetic stirrers are arranged at the bottoms of the biological cathode chamber 1, the anode chamber 2 and the chemical cathode chamber 3 or a stirrer is added in the chambers; the other is the same as in the first or second embodiment.
The mixing of the liquid in each chamber is enhanced by the stirrer, and the inhibition of the microbial activity caused by the accumulation of local substances is reduced.
The fourth concrete implementation mode: the difference of the embodiment from the first to the third embodiment is that the heat preservation devices are arranged outside the biological cathode chamber 1, the anode chamber 2 and the chemical cathode chamber 3, wherein the heat preservation devices are water baths or heat preservation cotton; the others are the same as in one of the first to third embodiments.
The temperature of the system can be conveniently controlled by utilizing the heat preservation effect of the heat preservation layer according to the temperature control requirement of the system (mainly according to the optimum temperature adjustment of the growth of the aeration biological catalytic activity bacteria and the electrochemical activity bacteria), so that the microorganisms are in the optimum temperature condition.
The fifth concrete implementation mode: the method for simultaneously treating the sludge and the electroplating wastewater of the electroplating industrial park by utilizing the device of the first embodiment comprises the following steps:
firstly, nutrient solution is added into a biological cathode chamber 1 as biological cathode electrolyte, sludge of a sewage treatment plant in an electroplating industrial park is added into an anode chamber 2 as an anode substrate, and electroplating wastewater is added into a chemical cathode chamber 3 as chemical cathode electrolyte;
and secondly, keeping the temperature of the biological cathode chamber 1, the anode chamber 2 and the chemical cathode chamber 3 at 20-40 ℃, starting the aeration device 1-2 in the biological cathode chamber 1, treating, changing half of nutrient solution and electroplating wastewater every 2-5 days, and changing residual sludge every 5-10 days to finish the treatment of sludge and electroplating wastewater in the electroplating industrial park.
The sixth specific implementation mode: the difference between the fifth embodiment and the fifth embodiment is that the sludge of the sewage treatment plant of the electroplating industrial park is domestic sludge, industrial sludge or a mixture of domestic sludge and industrial sludge. The rest is the same as the fifth embodiment.
The seventh embodiment: the fifth or sixth embodiment is different from the fifth or sixth embodiment in that: the compositions of the nutrient solution are shown in the following table 1, and the compositions of the trace elements are shown in the following table 2; the other is the same as the fifth or sixth embodiment.
TABLE 1 composition of nutrient solutions
Figure BDA0001386261340000051
TABLE 2 composition and ratio of trace element solution
Nitrilotriacetic acid MgSO4 MnSO4·H2O NaCl CuSO4·5H2O KAl(SO4)2
1.0-3.0g/L 1.0-3.0g/L 0.2-0.8g/L 1.0-3.0g/L 0.01-0.02g/L 0.01-0.05g/L
H3BO3 FeSO4·7H2O CaCl2·2H2O CoCl2·6H2O ZnSO4·7H2O Na2MoO4
0.01-0.02g/L 0.1-0.2g/L 0.1-0.2g/L 0.1-0.2g/L 0.1-0.2g/L 0.01-0.02g/L
The specific implementation mode is eight: this embodiment is different from the fifth to seventh embodiments in that Cr is contained6+The pretreatment method of the electroplating wastewater comprises the following steps: to Cr6+Adding sulfuric acid into the electroplating wastewater with the concentration of 50-300 mg/L to adjust the pH value to 1-2, adding sufficient hydrogen peroxide, and uniformly stirring, so as to oxidize and break the complexing agent, thereby completing pretreatment. The rest is the same as one of the fifth to seventh embodiments.
Because a large amount of complexing agent added in the electroplating process can combine with metal ions to reduce the concentration of the metal ions in the electroplating wastewater, various metal ions need to be replaced before the electroplating wastewater is treated. The present embodiment utilizes Cr under acidic conditions6+The strong oxidizing property of the catalyst and the oxidizing property of the hydrogen peroxide break the complexation, and various metal ions are replaced to be convenient to participate in the reaction.
The beneficial effects of the invention were verified by the following tests:
test 1: the experimental method for simultaneously treating the sludge and the electroplating wastewater in the park for the electroplating industrial park comprises the following steps:
firstly, preparation work: sealing 2L of anaerobic sludge generated by a sewage treatment plant in an electroplating industrial park, and storing at the temperature of 4-15 ℃ for 3 days for acclimatization; the graphite brush electrode material is conductive carbon fiber, which is washed by water before use and then respectively soaked by 1mol/L HCl solution and 1mol/L NaOH solutionSoaking for 2h to remove impurities on the surface of the electrode material, and finally soaking for 5h with deionized water for later use; the proton exchange membrane is firstly used with 30 percent of H before use2O2Boiling for 30min, respectively soaking for 2h by using 1mol/L HCl and 1mol/L NaOH solution respectively to remove pollutants and impurities on the surface of the membrane, and finally soaking for 5h by using deionized water for later use; cr in electroplating wastewater6+The concentration is 100mg/L, the electroplating wastewater is added with sulfuric acid to adjust the pH value to 2, and then sufficient hydrogen peroxide is added and stirred uniformly, so that the complexing agent is oxidized and broken, and the pretreatment is finished;
secondly, building a processing device: the treatment device consists of a biological cathode chamber 1, an anode chamber 2, a chemical cathode chamber 3, an external accumulator or electric appliance 4 and a proton exchange membrane 5; wherein the anode chamber 2 is positioned between the biological cathode chamber 1 and the chemical cathode chamber 3, and the biological cathode chamber 1 and the anode chamber 2 and the chemical cathode chamber 3 are separated by proton exchange membranes 5; the three chambers are all square spaces with equal volumes and surrounded by organic glass, a first graphite brush electrode 1-1 and an aeration device 1-2 are arranged in the biological cathode chamber 1, carbon granules 1-3 are filled in the biological cathode chamber 1, a first water outlet hole 1-4 is arranged at the bottom of the side wall of the biological cathode chamber 1, and a first air hole 1-5 is arranged at the top of the biological cathode chamber 1; a second graphite brush electrode 2-1 and a reference electrode 2-2 are arranged in the anode chamber 2, a second water outlet hole 2-3 is arranged at the bottom of the side wall of the anode chamber 2, and a second air hole 2-4 is arranged at the top of the anode chamber 2; a third graphite brush electrode 3-1 is arranged in the chemical cathode chamber 3, a third water outlet hole 3-2 is arranged at the bottom of the side wall of the chemical cathode chamber 3, and a third air hole 3-3 is arranged at the top of the chemical cathode chamber 3; a first graphite brush electrode 1-1 in the biological cathode chamber 1 and a third graphite brush electrode 3-1 in the chemical cathode chamber 3 are connected by a lead and then connected with a second graphite brush electrode 2-1 in the anode chamber 2 through an external accumulator or an electrical appliance 4 to form a closed loop; the arrangement of the parallel electrodes is beneficial to improving the electron transfer efficiency between the electrode chambers and reducing the direct mutual interference of the chemical cathode and the biological cathode; the reference electrode and the anode and the cathode of the reactor are connected into a voltage collector together for monitoring the electrochemical capacity;
thirdly, starting:
(1) adding the domesticated anaerobic sludge into the anode chamber 2 of the treatment device in the step two, and sealing; biological catholyte (namely nutrient solution) and a small amount of garden soil are added into the biological cathode chamber 1 and the chemical cathode chamber 3 to serve as soil for inoculation; then connecting a potential collector, turning on an aeration pump, and starting culture; wherein the composition of the biological catholyte is shown in table 3 below, and the composition of the trace elements is shown in table 4 below;
table 3 composition of biocatholytic solution:
NH4Cl K2HPO4 MgSO4 KCl KH2PO4 Fe2(SO4)3 yeast powder Trace elements
1.0g/L 1.2g/L 0.5g/L 0.5g/L 0.14g/L 0.01g/L 0.02g/L 10mL/L
Table 4 trace element solution ratio:
nitrilotriacetic acid MgSO4 MnSO4·H2O NaCl CuSO4·5H2O KAl(SO4)2
1.7g/L 1.6g/L 0.37g/L 1.5g/L 0.01g/L 0.02g/L
H3BO3 FeSO4·7H2O CaCl2·2H2O CoCl2·6H2O ZnSO4·7H2O Na2MoO4
0.01g/L 0.1g/L 0.1g/L 0.1g/L 0.1g/L 0.01g/L
(2) Replacing half of the biological catholyte in the biological cathode chamber 1 and the biological catholyte in the chemical cathode chamber 3 every 2 days, replacing anaerobic sludge in the anode chamber 2 every 5 days, culturing for two weeks, and keeping the battery potential to be maximum and stable for one day, wherein aeration biological catalytic active bacteria are attached to the first graphite brush electrode 1-1 and the carbon granules 1-3 in the biological cathode chamber 1; electrochemical active bacteria are attached to a second graphite brush electrode 2-1 in the anode chamber 2; aerating biological catalytic active bacteria are attached to a third graphite brush electrode 3-1 in the chemical cathode chamber 3, and the start is successful;
and fourthly, simultaneously treating the park sludge and electroplating wastewater in the electroplating industrial park:
(1) taking out the aeration head in the chemical cathode chamber 3, replacing the third graphite brush electrode 3-1 in the chemical cathode chamber 3 with the graphite brush which is processed in the first step and has no bacteria adhesion, and replacing the biological catholyte in the graphite brush with the Cr-containing graphite brush which is preprocessed in the first step6+Electroplating wastewater with the concentration of 100 mg/L;
(2) keeping the temperature of the biological cathode chamber 1, the anode chamber 2 and the chemical cathode chamber 3 at 30 ℃; starting an aeration device 1-2 in the biological cathode chamber 1; replacing half of the biological catholyte in the biological cathode chamber 1 every 2 days; changing the anaerobic sludge in the anode chamber 2 every 5 days, monitoring the Cr in the chemical cathode chamber 36+Replacing electroplating wastewater under the condition of reduced concentration, and simultaneously measuring the supernatant COD and the total sludge COD of the anode sludge; and finishing the treatment of sludge and electroplating wastewater in the electroplating industrial park.
And (3) comparison test: a two-compartment microbial fuel cell was operated according to the procedure of example 4 of the specification of chinese patent CN104386826A, and the cell was operated under the same environmental conditions as the three-compartment treatment apparatus of test 1, ensuring comparability of the experimental results.
The treatment effects of test 1 and the comparative test are as follows:
in Cr6+In the aspect of degradation effect, the three-chamber reactor in the test has better reduction degradation effect, and the degradation contains Cr6+The peak degradation speed of 100mg/L electroplating wastewater in water distribution reaches 37.4 mg/L.h, and the Cr content in the electroplating wastewater is reduced within 48h6+Degrading the electroplating wastewater of 100mg/L to Cr6+0.78mg/L, the degradation rate is 99.22%, the concentration of the electroplating wastewater in 72h is 0.17mg/L, and the degradation rate is 99.83%. In order to ensure high degradation degree and simultaneously minimize the use of Cr, the proposal is that Cr in the electroplating wastewater is used6+The degradation time of different batches with different concentrations is set within 48 h. Double-chamber anaerobic reactor operating under the same condition for degrading Cr-containing substances6+The peak speed of water distribution of the electroplating wastewater of 100mg/L is 18.2 mg/L.h, and the time of 48h is to contain Cr6+Degrading the electroplating wastewater of 100mg/L to 29.89mg/L, and carrying out the experiment for 78h to obtain Cr6+The concentration is 17.91mg/L, the degradation rate is 82.09%, and the degradation is slow in the later period.
In the aspect of operation stability, the three-chamber reactor in the test has stronger interference resistance in the reaction process, the battery potential of the three-chamber system is stabilized above 0.85V, the cathode potential is about 0.6V, and the anode potential is about-0.2V in the reaction process. And the cell potential of the double-chamber system is gradually reduced to 0.3V from 0.8V in the initial stage along with the reduction of the hexavalent chromium concentration along with the progress of the hexavalent chromium degradation. Meanwhile, the activity of the electrochemically active bacteria at the anode of the dual-chamber system is gradually reduced, and about 3 days is required for the degradation activity to be recovered after the chromium-containing wastewater is replaced.
In addition, the three-chamber reactor of this experiment had a certain sludge stabilization effect. Within 2 days, the TCOD degradation of the anode sludge is 13333mgO2The value of/L is changed to 10688mgO2L, the sludge degradation rate is 20 percent. The data of experimental implementation proves that the three-chamber reactor of the experiment can obviously improve the speed and the operation stability of the hexavalent chromium electroplating wastewater degradation.
Test 2: the difference between the test and the test 1 is that the electroplating wastewater in the fourth step is Cu-containing electroplating wastewater2+Wastewater with a concentration of 100 mg/L. The rest was the same as in test 1.
Test Cu2+Data on recovery of the effect, Cu in a three-compartment reactor in 24h2+Degrading 100mg/L wastewater to Cu2+0.32mg/L, the degradation rate is 99.68 percent, and the average degradation rate is 4.15 mg/L.h. Cu-containing degradation in a double-chamber reactor operated under the same conditions2+100mg/L of wastewater is degraded to contain Cu within 24 hours2+16.15mg/L, the degradation rate is 83.85%, and the later degradation is slower.
The total sludge COD degradation data of the anode chamber of the three-chamber reactor is that within 24 hours, the anode sludge TCOD degradation is 14300mgO2The ratio of/L to 12880mgO2L, the sludge degradation rate is 10 percent. The data of experimental implementation prove that the three-chamber reactor of the experiment can obviously improve the degradation of Cu2+The rate of wastewater and the operating stability.
Test 3: the difference between the test and the test 1 is that the electroplating wastewater in the fourth step is Ni-containing2+Wastewater with a concentration of 200 mg/L. The rest was the same as in test 1.
This test Ni2+Data on recovery effectiveness, the three-compartment reactor in 48h will contain Ni2+200mg/L of wastewater is degraded to contain Ni2+31.32mg/L, the degradation rate is 84.34 percent, and the average degradation rate is 3.51 mg/L.h. Ni-containing degradation in a double-chamber reactor operated under the same conditions2+100mg/L of wastewater is degraded to contain Ni within 48 hours2+70.06mg/L, the degradation rate is 64.97%, and the degradation is slower in the later period.
The total sludge COD degradation data of the anode chamber of the three-chamber reactor is that within 48 hours, the TCOD degradation of the anode sludge is 15750mgO2The value of/L is changed into 12452mgO2L, the sludge degradation rate is 21 percent. The data of experimental implementation prove that the three-chamber reactor of the experiment can obviously improve the degradation of Ni2+The rate of wastewater and the operating stability.
Test 4: the difference between the test and the test 1 is that the electroplating wastewater in the fourth step is Zn-containing2+Wastewater with a concentration of 1000 mg/L. The rest was the same as in test 1.
This test Zn2+Data on recovery of the effect, the three-compartment reactor in 48h will contain Zn2+Degrading the wastewater of 1000mg/L to Zn2+660.4mg/L, the degradation rate is 33.96 percent, and the product is degraded to content within 96 hoursZn2+593.7 mg/L. Zn-containing degradation in a double-chamber reactor operated under the same conditions2+1000mg/L of wastewater is degraded to contain Zn within 48h2+734.7mg/L, the degradation rate is 26.53%, and the degradation is slower in the later period.
The total sludge COD degradation data of the anode chamber of the three-chamber reactor is that within 48 hours, the anode sludge TCOD degradation is 13195mgO2The ratio of/L to 9007mgO2L, the sludge degradation rate is 31.7 percent. The data of the experiment prove that the three-chamber reactor of the experiment can improve the degradation of Zn to a certain extent2+The rate of wastewater.
Test 5: the difference between the test and the test 1 is that the electroplating wastewater in the fourth step is Cd-containing electroplating wastewater2+Wastewater with a concentration of 100 mg/L. The rest was the same as in test 1.
This test of Cd2+Data on recovery of the effect, Cd content in the 48h three-chamber reactor2+Degrading 100mg/L wastewater to contain Cd2+28.20mg/L, the degradation rate is 71.80 percent, and the average degradation rate is 1.50 mg/L.h. Degradation of Cd-containing materials in a double-chamber reactor operated under the same conditions2+Degrading 100mg/L wastewater to Cd in 48h2+44.73mg/L, the degradation rate is 55.27%, and the degradation is slower in the later period.
The total sludge COD degradation data of the anode chamber of the three-chamber reactor is that within 48 hours, the anode sludge TCOD degradation is carried out by 14170mgO2changing/L to 11900mgO2L, the sludge degradation rate is 16%. The data of experimental implementation prove that the three-chamber reactor of the experiment can obviously improve the degradation of Cd2+The rate of wastewater and the operating stability.
Test 6: the difference between the test and the test 1 is that the electroplating wastewater in the fourth step is Cr-containing electroplating wastewater6+And Cu2+Two kinds of metal ions, each of which has a concentration of 100mg/L of wastewater. The rest was the same as in test 1.
According to the data of the metal reduction effect in the test, the three-chamber reactor in 24h degrades the metal wastewater to Cu2+0.29mg/L of Cr6+5.84mg/L, the degradation rates are respectively 99.71 percent and 94.16 percent; when the reaction is carried out for 48h, Cu2+Trace, concentration about 0.10mg/L, Cr6+The concentration is 0.38mg/L, and the degradation rates are 99.9% and 99.62%, respectively. Is a single metalIons of Cr6+And Cu2+The electroplating wastewater has more efficient reduction performance.
The total sludge COD degradation data of the anode chamber of the three-chamber reactor is that within 48 hours, the anode sludge TCOD degradation is carried out by 16620mgO2The ratio of/L was 12130mgO2L, the sludge degradation rate is 27 percent.

Claims (8)

1. A device for simultaneously treating park sludge and electroplating wastewater in an electroplating industrial park is characterized by comprising a biological cathode chamber (1), an anode chamber (2), a chemical cathode chamber (3), an external electrical storage or appliance (4) and a proton exchange membrane (5); wherein the anode chamber (2) is positioned between the biological cathode chamber (1) and the chemical cathode chamber (3), and the biological cathode chamber (1) and the anode chamber (2) and the chemical cathode chamber (3) are separated by proton exchange membranes (5); a first graphite brush electrode (1-1) and an aeration device (1-2) are arranged in the biological cathode chamber (1), carbon granules (1-3) are filled in the biological cathode chamber (1), a first water outlet hole (1-4) is formed in the bottom of the side wall of the biological cathode chamber (1), and a first air hole (1-5) is formed in the top of the biological cathode chamber (1); aeration biological catalytic activity bacteria are attached to the first graphite brush electrode (1-1) and the carbon particles (1-3); a second graphite brush electrode (2-1) and a reference electrode (2-2) are arranged in the anode chamber (2), a second water outlet hole (2-3) is formed in the bottom of the side wall of the anode chamber (2), and a second air hole (2-4) is formed in the top of the anode chamber (2); electrochemical active bacteria are attached to the second graphite brush electrode (2-1); a third graphite brush electrode (3-1) is arranged in the chemical cathode chamber (3), and no bacteria is attached to the third graphite brush electrode (3-1); a third water outlet hole (3-2) is formed in the bottom of the side wall of the chemical cathode chamber (3), and a third air hole (3-3) is formed in the top of the chemical cathode chamber (3); a first graphite brush electrode (1-1) in the biological cathode chamber (1) and a third graphite brush electrode (3-1) in the chemical cathode chamber (3) are connected by a lead and then connected with a second graphite brush electrode (2-1) in the anode chamber (2) through an external electrical storage device or an electrical appliance (4) to form a closed loop.
2. An apparatus for simultaneous treatment of sludge and electroplating wastewater of a park for electroplating industrial park according to claim 1, characterized in that the biological cathode chamber (1) and the chemical cathode chamber (3) are rectangular or cylindrical.
3. An apparatus for simultaneous treatment of sludge and electroplating wastewater of a park for electroplating industrial park according to claim 1 or 2, characterized in that a magnetic stirrer is provided at the bottom of the biological cathode chamber (1), the anode chamber (2) and the chemical cathode chamber (3) or a stirrer is added in the chamber.
4. The apparatus for simultaneous treatment of sludge and electroplating wastewater of industrial park for electroplating according to claim 1 or 2, characterized in that an insulation means is provided outside the biological cathode chamber (1), the anode chamber (2) and the chemical cathode chamber (3), wherein the insulation means is a water bath or insulation cotton.
5. A method for simultaneously treating sludge and electroplating wastewater of an electroplating industrial park by using the device of claim 1, which is characterized by comprising the following steps:
firstly, nutrient solution is added into a biological cathode chamber (1) as biological catholyte, sludge of a sewage treatment plant in an electroplating industrial park is added into an anode chamber (2) as an anode substrate, and electroplating wastewater is added into a chemical cathode chamber (3) as chemical catholyte;
and secondly, keeping the temperature of the biological cathode chamber (1), the anode chamber (2) and the chemical cathode chamber (3) at 20-40 ℃, starting an aeration device (1-2) in the biological cathode chamber (1) for treatment, changing half of nutrient solution and electroplating wastewater every 2-5 days, and changing residual sludge every 5-10 days to finish the treatment of sludge and electroplating wastewater in the electroplating industrial park.
6. The method for simultaneously treating sludge and electroplating wastewater of an electroplating industrial park according to claim 5, wherein the sludge of the sewage treatment plant of the electroplating industrial park in the step one is domestic sludge, industrial sludge or a mixture of domestic sludge and industrial sludge.
7. Simultaneous treatment of sludge from electroplating industrial park according to claim 5 or 6And a method for producing electroplating wastewater, characterized in that the electroplating wastewater contains Cr6+、Cu2+、Ni2+、Zn2+And/or Cd2+。
8. The method for simultaneous treatment of sludge and wastewater from electroplating industrial park according to claim 7, characterized in that it contains Cr6+The pretreatment method of the electroplating wastewater comprises the following steps: to Cr6+Adding sulfuric acid into the electroplating wastewater with the concentration of 50-300 mg/L to adjust the pH value to 1-2, adding sufficient hydrogen peroxide, and uniformly stirring, so as to oxidize and break the complexing agent, thereby completing pretreatment.
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