CN111847626B - Use method of device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method - Google Patents
Use method of device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method Download PDFInfo
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Abstract
A method for using a device for pretreating complex heavy metals in electroplating cleaning wastewater by using a catalytic oxidation method relates to a method for using a device for pretreating electroplating cleaning wastewater. The invention aims to solve the technical problem that the existing complex heavy metal has poor degradation effect. The oxidation desludging pool is provided with the three folding plates, and the inlet water flows in a zigzag way among the three folding plates to form a plurality of small vortexes, so that the reaction efficiency of the catalyst and the oxidant is improved, and the reaction rate between singlet oxygen and pollutants generated by the interaction of the catalyst and the oxidant is increased, so that the singlet oxygen and the pollutants are fully reacted; the invention provides the concept of 'multi-stage reaction and relay oxidation', and the medicine adding ports are arranged in the first three intervals; the double-effect recovery tank is formed by combining the principles of an electrolytic gas floatation method and an electrolytic reduction method, and can simultaneously and efficiently recover the catalyst and the complex heavy metal simple substance in the electroplating cleaning wastewater to be treated.
Description
Technical Field
The invention relates to a use method of a device for pretreating electroplating cleaning wastewater.
Background
The complex-state heavy metal wastewater refers to wastewater containing heavy metal ions and complexing agents (such as Ethylene Diamine Tetraacetic Acid (EDTA), citric acid, tartaric acid and the like), the heavy metals receive electron pairs from some functional groups (such as carboxyl, amino, phenolic hydroxyl, sulfydryl and the like) to form a stable complex state, and the wastewater discharged by the tanning metal smelting industry of the printing and dyeing industry of the electroplating industry contains a large amount of complex-state heavy metals. The method is characterized in that about 400 hundred million tons of industrial wastewater is generated every year in China, wherein only electroplating wastewater accounts for 10% of the total amount of the industrial wastewater, compared with free heavy metal ions, the wastewater discharged by most processes in the electroplating industry contains complex heavy metals, the complex heavy metals have higher stability and more complex forms, the EDTA which is most widely researched at present is taken as an example, the ligand and the heavy metals usually exist in a chelating form, the chelating structure is very stable, the characteristics of organic matters and the heavy metals are simultaneously achieved, the toxicity is stronger, the migration is easier, and the ligand is difficult to remove by traditional means such as precipitation adsorption and the like. The complex heavy metal has strong stability, and can seriously threaten the water environment if not treated in time, so the method is a great problem in the field of industrial wastewater treatment, the development of an efficient complex heavy metal degradation process has important significance in the field of environment, and the resource recovery of degraded metal ions has more economic significance.
As a classical carbon material, nanodiamond is widely studied in the fields of biosensors, targeted drug therapy, and the like. But has not received much attention in the environmental field. However, in recent years, carbon materials represented by carbon nanotubes have been attracting much attention in catalyzing persulfate to degrade organic substances, and thus nanodiamonds of the same carbon family have also been attracting much attention. At present, in the field of carbon catalysis of persulfate, untreated nano-diamond often cannot show a good catalytic effect. Therefore, studies on nanodiamonds have been focused on modifying them by various methods, such as high-temperature calcination, to change the types and amounts of functional groups on the surface, but the difference in temperature changes the physicochemical properties of nanodiamonds? What is the temperature the optimum processing temperature? How does the reaction mechanism of diamond change at different temperatures? What is the state of graphitized and non-graphitized nanodiamonds more utilizing catalytic persulfate? None of these problems has been systematically investigated. Therefore, based on the scientific problems, it is important to explore how to optimize the treatment conditions and the corresponding internal mechanisms to obtain the optimal nano-diamond modification conditions.
Disclosure of Invention
The invention provides a use method of a device for pretreating complex heavy metal in electroplating cleaning wastewater by using a catalytic oxidation method, aiming at solving the technical problem that the existing complex heavy metal has poor degradation effect.
The device for pretreating complex heavy metals in electroplating cleaning wastewater by using a catalytic oxidation method comprises an oxidation desludging pool 1, a double-effect recovery pool 2, a first folding plate 3, a second folding plate 4, a third folding plate 5, a cathode plate 6, an anode plate 7, a direct-current power supply 8 and a water pipe 9;
the oxidation desludging pool 1 is of a cuboid structure, and 4 side walls are respectively a first side wall 1-5, a second side wall 1-6, a third side wall 1-7 and a fourth side wall 1-8; the first side wall 1-5 and the second side wall 1-6 are opposite faces, the third side wall 1-7 and the fourth side wall 1-8 are opposite faces, and the second side wall 1-6 and the third side wall 1-7 are perpendicular to each other; a first water inlet 1-1 is arranged on the first side wall 1-5, the height of the first water inlet 1-1 is half of the height of the oxidation desludging pond 1, and the first water inlet 1-1 is relatively close to a fourth side wall 1-8; a first folding plate 3, a second folding plate 4 and a third folding plate 5 are fixed on an inner bottom plate of the oxidation de-winding pool 1, and the first folding plate 3, the second folding plate 4 and the third folding plate 5 are the same in height and are 2/3-3/4 of the height of the oxidation de-winding pool 1; the first folded plate 3, the second folded plate 4 and the third folded plate 5 are arranged in parallel, and the length direction of the first folded plate 3 is vertical to the water inlet direction of the first water inlet 1-1; the three folded plates are all composed of a plurality of straight plates with mutually included angles of alpha, and the alpha is 85-90 degrees; one side surface of the first folding plate 3 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the first folding plate 3 and the inner wall of the third side wall 1-7; one side surface of the second folding plate 4 is fixed on the inner walls of the third side walls 1-7, and a gap is reserved between the other side surface of the second folding plate 4 and the inner walls of the fourth side walls 1-8; one side surface of the third folding plate 5 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the third folding plate 5 and the inner wall of the third side wall 1-7; the upper parts of the fourth side walls 1-8 are respectively provided with a first medicine adding opening 1-3 and a second medicine adding opening 1-4, the first medicine adding opening 1-3 and the second medicine adding opening 1-4 are equal in height and the height is larger than that of the first folded plate 3; the first medicine adding port 1-3 is arranged between the first side wall 1-5 and the first folding plate 3, and the second medicine adding port 1-4 is arranged between the second folding plate 4 and the third folding plate 5; a third medicine adding opening 1-2 is formed in the upper portion of the third side wall 1-7, the third medicine adding opening 1-2 and the second medicine adding opening 1-4 are equal in height, and the third medicine adding opening 1-2 is formed between the second folding plate 4 and the first folding plate 3; a first water outlet is formed in the bottom of the second side wall 1-6 and is relatively close to the fourth side wall 1-8;
a negative plate 6 and an anode plate 7 are arranged inside the double-effect recovery tank 2, a direct-current power supply 8 is arranged outside the double-effect recovery tank 2, the negative electrode of the direct-current power supply 8 is connected with the negative plate 6, and the positive electrode of the direct-current power supply 8 is connected with the negative plate 7; the lower part of the side wall of the double-effect recovery tank 2 is provided with a second water inlet and a second water outlet 2-1, the second water inlet is communicated with the first water outlet of the oxidation and decomplexation tank 1 through a water pipe 9, and the side wall where the second water inlet and the second water outlet 2-1 are located is two opposite side walls.
The use method of the device for pretreating the complex heavy metal in the electroplating cleaning wastewater by using the catalytic oxidation method comprises the following steps:
firstly, adding an oxidant and a catalyst into an oxidation decomplexation pool 1 through a first dosing port 1-3, a second dosing port 1-4 and a third dosing port 1-2, wherein the oxidant is solid persulfate, and the catalyst is solid graphitized nano-diamond; then, the electroplating cleaning wastewater to be treated enters an oxidation desludging pool 1 through a first water inlet 1-1 after being collected, the water level is lower than the height of a first folding plate 3, the concentrations of oxidants added into three dosing ports in the electroplating cleaning wastewater to be treated are 30.738-153.69 g/L, and the concentrations of catalysts added into the three dosing ports in the electroplating cleaning wastewater to be treated are 0.1-0.2 g/L;
the treated wastewater flows out of a first water outlet of the oxidation de-complexing pool 1 through a water pipe 9 and then enters the double-effect recovery pool 2 through a second water inlet of the double-effect recovery pool 2, a direct-current power supply 8 is started, voltage is firstly adjusted to the reduction potential of complex-state heavy metals in the electroplating cleaning wastewater to be treated, the heavy metals are collected on a cathode plate 7, the voltage is adjusted to 1.23V after the heavy metals are completely reduced, micro bubbles can be generated on an anode plate 6, the catalyst is attached to the bubbles and floats to the liquid surface for recovery through the micro bubbles, therefore, a double-effect recovery system for recovering the catalyst and recovering metal resources is realized, and the treated wastewater is discharged through a second water outlet 2-1.
The principle and the beneficial effects of the invention are as follows:
the oxidation desludging pool 1 is provided with three folded plates, the oxidation desludging pool 1 is divided into four sections, the water flow speed of the four sections from water inlet to water outlet is reduced in sequence, the included angle alpha of the folded plates is about 90 degrees, and the inlet water flows in a zigzag way among the folded plates to form a plurality of small vortexes, so that the reaction efficiency of a catalyst and an oxidant is improved, and the reaction rate between singlet oxygen and pollutants generated by the interaction of the catalyst and the oxidant is increased, so that the reaction is fully performed; because the survival time of singlet oxygen in water is extremely short, the invention provides the concept of 'multi-stage reaction and relay oxidation', the medicine adding ports are arranged in the first three intervals, the graphitized nano-diamond catalyst and the monopersulfate oxidant are both added with solid, and the medicine adding amount is controlled to ensure that the concentrations of the catalyst and the oxidant are both in the most efficient stage;
the device is formed by coupling the principles of an electrolytic gas floatation method and an electrolytic reduction method, and can simultaneously and efficiently recover a catalyst and complex heavy metal simple substances in electroplating cleaning wastewater to be treated. The main body is a direct current electrolytic cell, the cathode plate 7 is an inert carbon electrode (glassy carbon electrode or graphite), the cathode plate 7 is a stainless steel plate, firstly, the voltage is adjusted to the reduction potential of the complex heavy metal in the electroplating cleaning wastewater to be treated, heavy metals are collected on the cathode plate 7, when the reduction of the heavy metals is finished, the voltage is adjusted to 1.23V (the voltage required by the electrolyzed water), at the moment, the metal ions dissociated from the complex state are reduced on the cathode plate 6 and collected on the cathode plate 6, when the metal ions in the solution are completely recovered, the hydrogen ions in the water are reduced to hydrogen gas to be separated out, meanwhile, an oxidation reaction is generated on the anode plate 7 to generate micro bubbles 10 such as oxygen gas and the like, the micro-bubbles 10 can make the nano-scale catalyst attached to the bubbles 10 and float to the liquid surface for recovery, thereby realizing a double-effect recovery system for recovering the catalyst and the metal resources.
Drawings
FIG. 1 is a schematic diagram of an apparatus for pre-treating complex heavy metals in electroplating cleaning wastewater by catalytic oxidation according to a first embodiment; region a is an enlarged view of the area of the bubble 10 near the anode plate 7, and Δ is the catalyst; region B is an enlarged view of the area of the bubble 10 near the cathode plate 6, Δ is the catalyst;
FIG. 2 is a top view of the oxidative de-complexation cell 1 of FIG. 1;
FIG. 3 is a graph showing the effect of the copper complex degradation rate and the copper recovery rate in test two;
fig. 4 is TEM images of nanodiamonds of different graphitization degrees.
Detailed Description
The first embodiment is as follows: the embodiment is a device for pretreating complex heavy metals in electroplating cleaning wastewater by using a catalytic oxidation method, and as shown in fig. 1-2, the device specifically comprises an oxidation desludging pool 1, a double-effect recovery pool 2, a first folding plate 3, a second folding plate 4, a third folding plate 5, a cathode plate 6, an anode plate 7, a direct-current power supply 8 and a water pipe 9;
the oxidation desludging pool 1 is of a cuboid structure, and 4 side walls are respectively a first side wall 1-5, a second side wall 1-6, a third side wall 1-7 and a fourth side wall 1-8; the first side wall 1-5 and the second side wall 1-6 are opposite faces, the third side wall 1-7 and the fourth side wall 1-8 are opposite faces, and the second side wall 1-6 and the third side wall 1-7 are perpendicular to each other; a first water inlet 1-1 is arranged on the first side wall 1-5, the height of the first water inlet 1-1 is half of the height of the oxidation desludging pond 1, and the first water inlet 1-1 is relatively close to a fourth side wall 1-8; a first folding plate 3, a second folding plate 4 and a third folding plate 5 are fixed on an inner bottom plate of the oxidation de-winding pool 1, and the first folding plate 3, the second folding plate 4 and the third folding plate 5 are the same in height and are 2/3-3/4 of the height of the oxidation de-winding pool 1; the first folded plate 3, the second folded plate 4 and the third folded plate 5 are arranged in parallel, and the length direction of the first folded plate 3 is vertical to the water inlet direction of the first water inlet 1-1; the three folded plates are all composed of a plurality of straight plates with mutually included angles of alpha, and the alpha is 85-90 degrees; one side surface of the first folding plate 3 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the first folding plate 3 and the inner wall of the third side wall 1-7; one side surface of the second folding plate 4 is fixed on the inner walls of the third side walls 1-7, and a gap is reserved between the other side surface of the second folding plate 4 and the inner walls of the fourth side walls 1-8; one side surface of the third folding plate 5 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the third folding plate 5 and the inner wall of the third side wall 1-7; the upper parts of the fourth side walls 1-8 are respectively provided with a first medicine adding opening 1-3 and a second medicine adding opening 1-4, the first medicine adding opening 1-3 and the second medicine adding opening 1-4 are equal in height and the height is larger than that of the first folded plate 3; the first medicine adding port 1-3 is arranged between the first side wall 1-5 and the first folding plate 3, and the second medicine adding port 1-4 is arranged between the second folding plate 4 and the third folding plate 5; a third medicine adding opening 1-2 is formed in the upper portion of the third side wall 1-7, the third medicine adding opening 1-2 and the second medicine adding opening 1-4 are equal in height, and the third medicine adding opening 1-2 is formed between the second folding plate 4 and the first folding plate 3; a first water outlet is formed in the bottom of the second side wall 1-6 and is relatively close to the fourth side wall 1-8;
a negative plate 6 and an anode plate 7 are arranged inside the double-effect recovery tank 2, a direct-current power supply 8 is arranged outside the double-effect recovery tank 2, the negative electrode of the direct-current power supply 8 is connected with the negative plate 6, and the positive electrode of the direct-current power supply 8 is connected with the negative plate 7; the lower part of the side wall of the double-effect recovery tank 2 is provided with a second water inlet and a second water outlet 2-1, the second water inlet is communicated with the first water outlet of the oxidation and decomplexation tank 1 through a water pipe 9, and the side wall where the second water inlet and the second water outlet 2-1 are located is two opposite side walls.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the cathode plate 6 is a stainless steel plate. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the anode plate 7 is an inert carbon electrode. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the third difference between the present embodiment and the specific embodiment is that: the inert carbon electrode is a glassy carbon electrode or a graphite electrode. The rest is the same as the third embodiment.
The fifth concrete implementation mode: the embodiment is a use method of a device for pretreating complex heavy metals in electroplating cleaning wastewater by using a catalytic oxidation method, and the specific process is as follows:
firstly, adding an oxidant and a catalyst into an oxidation decomplexation pool 1 through a first dosing port 1-3, a second dosing port 1-4 and a third dosing port 1-2, wherein the oxidant is solid persulfate, and the catalyst is solid graphitized nano-diamond; then, the electroplating cleaning wastewater to be treated enters an oxidation desludging pool 1 through a first water inlet 1-1 after being collected, the water level is lower than the height of a first folding plate 3, the concentrations of oxidants added into three dosing ports in the electroplating cleaning wastewater to be treated are 30.738-153.69 g/L, and the concentrations of catalysts added into the three dosing ports in the electroplating cleaning wastewater to be treated are 0.1-0.2 g/L;
the treated wastewater flows out of a first water outlet of the oxidation de-complexing pool 1 through a water pipe 9 and then enters the double-effect recovery pool 2 through a second water inlet of the double-effect recovery pool 2, a direct-current power supply 8 is started, voltage is firstly adjusted to the reduction potential of complex-state heavy metals in the electroplating cleaning wastewater to be treated, the heavy metals are collected on a cathode plate 7, the voltage is adjusted to 1.23V after the heavy metals are completely reduced, micro bubbles can be generated on an anode plate 6, the catalyst is attached to the bubbles and floats to the liquid surface for recovery through the micro bubbles, therefore, a double-effect recovery system for recovering the catalyst and recovering metal resources is realized, and the treated wastewater is discharged through a second water outlet 2-1.
The principle and the beneficial effects of the embodiment are as follows:
in the embodiment, three folded plates are arranged in the oxidation desludging pool 1, the oxidation desludging pool 1 is divided into four sections, the water flow speed of the four sections is sequentially reduced from water inlet to water outlet, the included angle alpha of the folded plates is about 90 degrees, and the inlet water flows in a zigzag way among the folded plates to form a plurality of small vortexes, so that the reaction efficiency of a catalyst and an oxidant is improved, and the reaction rate between singlet oxygen and pollutants generated by the interaction of the catalyst and the oxidant is increased, so that the reaction is fully performed; because the survival time of singlet oxygen in water is extremely short, the invention provides the concept of 'multi-stage reaction and relay oxidation', the medicine adding ports are arranged in the first three intervals, the graphitized nano-diamond catalyst and the monopersulfate oxidant are both added with solid, and the medicine adding amount is controlled to ensure that the concentrations of the catalyst and the oxidant are both in the most efficient stage;
the device is formed by coupling the principles of an electrolytic gas floatation method and an electrolytic reduction method, and can simultaneously and efficiently recover a catalyst and complex heavy metal simple substances in electroplating cleaning wastewater to be treated. The main body is a direct current electrolytic cell, the cathode plate 7 is an inert carbon electrode (glassy carbon electrode or graphite), the cathode plate 7 is a stainless steel plate, firstly, the voltage is adjusted to the reduction potential of the complex heavy metal in the electroplating cleaning wastewater to be treated, collecting heavy metal on the cathode plate 7, adjusting the voltage to 1.23V (voltage required by water electrolysis) after the heavy metal is reduced, reducing the metal ions dissociated from the complex state on the cathode plate 6, collecting the metal ions on the cathode plate 6, when the metal ions in the solution are completely recovered, the hydrogen ions in the water are reduced to hydrogen gas to be separated out, meanwhile, an oxidation reaction is generated on the anode plate 7 to generate micro bubbles 10 such as oxygen gas and the like, the micro-bubbles 10 can make the nano-scale catalyst attached to the bubbles 10 and float to the liquid surface for recovery, thereby realizing a double-effect recovery system for recovering the catalyst and the metal resources.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the persulfate is one or a mixture of monopersulfate and peroxodisulfate. The rest is the same as the fifth embodiment.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the preparation method of the graphitized nano diamond comprises the following steps:
uniformly paving the nano-diamond powder in a quartz boat, wherein the thickness of the nano-diamond powder in the quartz boat is less than 1.5 cm; then placing the quartz boat in a tube furnace, and introducing argon into the tube furnace at the flow rate of 150 mL/min-200 mL/min for 20 min-30 mm;
keeping the flow rate of argon at 150-200 mL/min, raising the temperature of the tube furnace to 900 ℃ at a temperature rise rate of 5-10 ℃/min, and annealing for 2-3 h at 900 ℃ under the protection of argon;
and thirdly, naturally cooling to room temperature under the protection of argon gas to obtain the graphitized nano diamond.
The invention was verified with the following tests:
test one: the test is a device for pretreating complex heavy metals in electroplating cleaning wastewater by using a catalytic oxidation method, and as shown in fig. 1-2, the device specifically comprises an oxidation desludging pool 1, a double-effect recovery pool 2, a first folding plate 3, a second folding plate 4, a third folding plate 5, a cathode plate 6, an anode plate 7, a direct-current power supply 8 and a water pipe 9; the cathode plate 6 is a stainless steel plate; the anode plate 7 is a graphite electrode;
the oxidation desludging pool 1 is of a cuboid structure, and 4 side walls are respectively a first side wall 1-5, a second side wall 1-6, a third side wall 1-7 and a fourth side wall 1-8; the first side wall 1-5 and the second side wall 1-6 are opposite faces, the third side wall 1-7 and the fourth side wall 1-8 are opposite faces, and the second side wall 1-6 and the third side wall 1-7 are perpendicular to each other; a first water inlet 1-1 is arranged on the first side wall 1-5, the height of the first water inlet 1-1 is half of the height of the oxidation desludging pond 1, and the first water inlet 1-1 is relatively close to a fourth side wall 1-8; a first folding plate 3, a second folding plate 4 and a third folding plate 5 are fixed on an inner bottom plate of the oxidation desludging pool 1, and the first folding plate 3, the second folding plate 4 and the third folding plate 5 are the same in height and are 2/3-3/4 of the height of the oxidation desludging pool 1; the first folded plate 3, the second folded plate 4 and the third folded plate 5 are arranged in parallel, and the length direction of the first folded plate 3 is vertical to the water inlet direction of the first water inlet 1-1; the three folded plates are all composed of a plurality of straight plates with included angles alpha, and the alpha is 90 degrees; one side surface of the first folding plate 3 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the first folding plate 3 and the inner wall of the third side wall 1-7; one side surface of the second folding plate 4 is fixed on the inner walls of the third side walls 1-7, and a gap is reserved between the other side surface of the second folding plate 4 and the inner walls of the fourth side walls 1-8; one side surface of the third folding plate 5 is fixed on the inner wall of the fourth side wall 1-8, and a gap is reserved between the other side surface of the third folding plate 5 and the inner wall of the third side wall 1-7; the upper parts of the fourth side walls 1-8 are respectively provided with a first medicine adding opening 1-3 and a second medicine adding opening 1-4, the first medicine adding opening 1-3 and the second medicine adding opening 1-4 are equal in height and the height is larger than that of the first folded plate 3; the first medicine adding port 1-3 is arranged between the first side wall 1-5 and the first folding plate 3, and the second medicine adding port 1-4 is arranged between the second folding plate 4 and the third folding plate 5; a third medicine adding opening 1-2 is formed in the upper portion of the third side wall 1-7, the third medicine adding opening 1-2 and the second medicine adding opening 1-4 are equal in height, and the third medicine adding opening 1-2 is formed between the second folding plate 4 and the first folding plate 3; a first water outlet is formed in the bottom of the second side wall 1-6 and is relatively close to the fourth side wall 1-8;
a cathode plate 6 and an anode plate 7 are arranged inside the double-effect recovery tank 2, a direct-current power supply 8 is arranged outside the double-effect recovery tank 2, the cathode of the direct-current power supply 8 is connected with the cathode plate 6, and the anode of the direct-current power supply 8 is connected with the cathode plate 7; the lower part of the side wall of the double-effect recovery tank 2 is provided with a second water inlet and a second water outlet 2-1, the second water inlet is communicated with the first water outlet of the oxidation and decomplexation tank 1 through a water pipe 9, and the side wall where the second water inlet and the second water outlet 2-1 are located is two opposite side walls.
And (2) test II: the test is a use method of a device for pretreating complex heavy metal in electroplating cleaning wastewater by using a catalytic oxidation method in the first test, and the specific process is as follows:
firstly, adding an oxidant and a catalyst into an oxidation de-complexing pool 1 through a first dosing port 1-3, a second dosing port 1-4 and a third dosing port 1-2, wherein the oxidant is solid sodium monopersulfate, and the catalyst is solid graphitized nano-diamond; then, electroplating cleaning wastewater (EDTA-Cu) to be treated enters an oxidation desludging pool 1 through a first water inlet 1-1 after being collected, the water level is lower than the height of a first folding plate 3, the concentrations of oxidants added into three dosing ports in the electroplating cleaning wastewater to be treated are 30.738-153.69 g/L, and the concentrations of catalysts added into the three dosing ports in the electroplating cleaning wastewater to be treated are 0.1-0.2 g/L;
the treated wastewater flows out of a first water outlet of the oxidation de-complexing pool 1 through a water pipe 9 and then enters the double-effect recovery pool 2 through a second water inlet of the double-effect recovery pool 2, a direct-current power supply 8 is started, the voltage is firstly adjusted to 0.341V of the reduction potential of the complex-state heavy metal copper in the electroplating cleaning wastewater to be treated, a copper simple substance is collected on a cathode plate 7, the voltage is adjusted to 1.23V after the copper is completely reduced, micro bubbles can be generated on an anode plate 6, the catalyst is attached to the bubbles and floats to the liquid surface to be recovered through the micro bubbles, therefore, a double-effect recovery system for recovering the catalyst and recovering metal resources is realized, and the treated wastewater is discharged through a second water outlet 2-1.
The principle and the beneficial effects of the test are as follows:
in the test, the oxidation desludging pool 1 is provided with three folded plates, the oxidation desludging pool 1 is divided into four sections, the water flow speed of the four sections is sequentially reduced from water inlet to water outlet, the included angle alpha of the folded plates is 90 degrees, the inlet water flows in a zigzag way among the folded plates to form a plurality of small vortexes, the reaction efficiency of a catalyst and an oxidant is improved, and the reaction rate between singlet oxygen and pollutants generated by the interaction of the catalyst and the oxidant is increased, so that the reaction is fully carried out; because the survival time of singlet oxygen in water is extremely short, the invention provides the concept of 'multi-stage reaction and relay oxidation', the medicine adding ports are arranged in the first three intervals, the graphitized nano-diamond catalyst and the monopersulfate oxidant are both added with solid, and the medicine adding amount is controlled to ensure that the concentrations of the catalyst and the oxidant are both in the most efficient stage;
the device is formed by coupling the principles of an electrolytic gas floatation method and an electrolytic reduction method, and can simultaneously and efficiently recover a catalyst and complex heavy metal simple substances in electroplating cleaning wastewater to be treated. The main body is a direct current electrolytic cell, the cathode plate 7 is an inert carbon electrode (glassy carbon electrode or graphite), the cathode plate 7 is a stainless steel plate, firstly, the voltage is adjusted to the reduction potential of the complex heavy metal in the electroplating cleaning wastewater to be treated, collecting heavy metal on the cathode plate 7, adjusting the voltage to 1.23V (voltage required by water electrolysis) after the heavy metal is reduced, reducing the metal ions dissociated from the complex state on the cathode plate 6, collecting the metal ions on the cathode plate 6, when the metal ions in the solution are completely recovered, the hydrogen ions in the water are reduced to hydrogen gas to be separated out, meanwhile, an oxidation reaction is generated on the anode plate 7 to generate micro bubbles 10 such as oxygen gas and the like, the micro-bubbles 10 can make the nano-scale catalyst attached to the bubbles 10 and float to the liquid surface for recovery, thereby realizing a double-effect recovery system for recovering the catalyst and the metal resources.
The preparation method of the graphitized nano diamond comprises the following steps:
uniformly paving the nano-diamond powder in a quartz boat, wherein the thickness of the nano-diamond powder in the quartz boat is less than 1.5 cm; then placing the quartz boat in a tube furnace, and introducing argon into the tube furnace at the flow rate of 150mL/min for 20 min;
and secondly, keeping the flow rate of argon at 150mL/min, raising the temperature of the tube furnace to 900 ℃ at the temperature rise rate of 5 ℃/min, and annealing for 2h at the temperature of 900 ℃ under the protection of argon.
Fig. 3 is an effect diagram of the degradation rate and the recovery rate of copper complex in the second test, the content of copper in a complex state is measured by sampling at the first water outlet of the oxidation desludging pool 1, and the degradation rate of the copper complex at the first water inlet 1-1 relative to the oxidation desludging pool 1 is calculated to reach 80%; the recovery rate of the complex state copper at the position 1-1 of the first water inlet 1 of the oxidation de-complexing pool 1 is 70 percent through the recovery, weighing and conversion of the copper on the cathode plate 6 of the double-effect recovery pool 2.
And drying and weighing the catalyst recovered from the double-effect recovery tank 2, and calculating to obtain a recovery rate of 62.4 percent relative to the total amount of the catalyst added at the three dosing ports in the oxidation de-complexation tank 1.
And (3) test III: the preparation method of the graphitized nano diamond in the test comprises the following steps:
uniformly paving 100mg of nano-diamond powder in a quartz boat, wherein the thickness of the nano-diamond powder in the quartz boat is less than 1.5 cm; then placing the quartz boat in a tube furnace, and introducing argon into the tube furnace at the flow rate of 150mL/min for 20 min;
keeping the flow rate of argon at 150mL/min, then raising the temperature of the tube furnace to 700 ℃ at the temperature rise rate of 5 ℃/min, and annealing for 2h at the temperature of 700 ℃ under the protection of argon;
and thirdly, naturally cooling to room temperature under the protection of argon gas to obtain the graphitized nano diamond.
And (4) testing: the experiment is different from the experiment in three ways: and secondly, keeping the flow rate of argon at 150mL/min, then raising the temperature of the tube furnace to 800 ℃ at the temperature rise rate of 5 ℃/min, and annealing for 2h at the temperature of 800 ℃ under the protection of argon. The rest were the same as in test three.
And (5) testing five: the experiment is different from the experiment in three ways: and secondly, keeping the flow rate of argon at 150mL/min, raising the temperature of the tube furnace to 900 ℃ at the temperature rise rate of 5 ℃/min, and annealing for 2h at the temperature of 900 ℃ under the protection of argon. The rest were the same as in test three.
And (6) testing six: the experiment is different from the experiment in three ways: and secondly, keeping the flow rate of argon at 150mL/min, raising the temperature of the tube furnace to 1000 ℃ at the temperature rise rate of 5 ℃/min, and annealing for 2h at the temperature of 1000 ℃ under the protection of argon. The rest were the same as in test three.
Test seven: the experiment is different from the experiment in three ways: and secondly, keeping the flow rate of argon at 150mL/min, then raising the temperature of the tube furnace to 1100 ℃ at the temperature raising rate of 5 ℃/min, and annealing for 2h at the temperature of 1100 ℃ under the protection of argon. The rest were the same as in test three.
Fig. 4 is TEM images of nanodiamonds of different graphitization degrees, in which a, b, c, d, e, and f represent graphitized nanodiamonds prepared in untreated nanodiamond powder, test three, test four, test five, test six, and test seven, respectively. As can be seen from the figure, the lattice change of the nanodiamond can be controlled by controlling the calcination temperature, and when the calcination temperature is 900 ℃, onion-like sp begins to appear on the surface of the nanodiamond 2 Carbon, which is sp 3 Most significant feature of graphitizationThe onion-like carbon grows with the increase of the calcination temperature, which shows that the graphitization degree is gradually increased.
Claims (4)
1. The use method of the device for pretreating the complex heavy metal in the electroplating cleaning wastewater by using the catalytic oxidation method is characterized by comprising the following steps of:
firstly, adding an oxidant and a catalyst into an oxidation decomplexing pool (1) through a first dosing port (1-3), a second dosing port (1-4) and a third dosing port (1-2), wherein the oxidant is solid persulfate, and the catalyst is solid graphitized nano-diamond; then the electroplating cleaning wastewater to be treated enters an oxidation de-complexing pool (1) through a first water inlet (1-1) after being collected, the water level is lower than the height of a first folded plate (3), the concentrations of oxidants added into three dosing ports in the electroplating cleaning wastewater to be treated are 30.738-153.69 g/L, and the concentrations of catalysts added into the three dosing ports in the electroplating cleaning wastewater to be treated are 0.1-0.2 g/L; the persulfate is one or a mixture of monopersulfate and peroxodisulfate;
the treated wastewater flows out of a first water outlet of the oxidation de-complexing pool (1) through a water pipe (9), then enters the double-effect recovery pool (2) through a second water inlet of the double-effect recovery pool (2), a direct-current power supply (8) is started, the voltage is firstly adjusted to the reduction potential of complex-state heavy metal in the electroplating cleaning wastewater to be treated, the heavy metal is collected on a cathode plate (6), the voltage is adjusted to 1.23V after the heavy metal is completely reduced, micro bubbles can be generated on an anode plate (7), the catalyst is attached to the bubbles and floats to the liquid surface to be recovered through the micro bubbles, so that a double-effect recovery system for recovering the catalyst and recovering metal resources is realized, and the treated wastewater is discharged through a second water outlet (2-1);
the preparation method of the graphitized nano diamond comprises the following steps:
uniformly paving nano diamond powder in a quartz boat, wherein the thickness of the nano diamond powder in the quartz boat is less than 1.5 cm; then placing the quartz boat in a tube furnace, and introducing argon into the tube furnace at the flow rate of 150 mL/min-200 mL/min for 20 min-30 mm;
keeping the flow rate of argon at 150-200 mL/min, raising the temperature of the tube furnace to 900 ℃ at a temperature rise rate of 5-10 ℃/min, and annealing for 2-3 h at 900 ℃ under the protection of argon;
naturally cooling to room temperature under the protection of argon gas to obtain graphitized nano diamond;
the device for pretreating the complex heavy metal in the electroplating cleaning wastewater by using the catalytic oxidation method consists of an oxidation de-complexing pool (1), a double-effect recovery pool (2), a first folded plate (3), a second folded plate (4), a third folded plate (5), a cathode plate (6), an anode plate (7), a direct-current power supply (8) and a water pipe (9);
the oxidation desludging pool (1) is of a cuboid structure, and 4 side walls are respectively a first side wall (1-5), a second side wall (1-6), a third side wall (1-7) and a fourth side wall (1-8); the first side wall (1-5) and the second side wall (1-6) are opposite faces, the third side wall (1-7) and the fourth side wall (1-8) are opposite faces, and the second side wall (1-6) and the third side wall (1-7) are perpendicular to each other; a first water inlet (1-1) is arranged on the first side wall (1-5), the height of the first water inlet (1-1) is half of the height of the oxidation desludging pool (1), and the first water inlet (1-1) is relatively close to the fourth side wall (1-8); a first folded plate (3), a second folded plate (4) and a third folded plate (5) are fixed on an inner bottom plate of the oxidation threshing pool (1), and the first folded plate (3), the second folded plate (4) and the third folded plate (5) are the same in height and are 2/3-3/4 of the height of the oxidation threshing pool (1); the first folded plate (3), the second folded plate (4) and the third folded plate (5) are arranged in parallel, and the length direction of the first folded plate (3) is vertical to the water inlet direction of the first water inlet (1-1); the three folded plates are all composed of a plurality of straight plates with mutually included angles of alpha, and the alpha is 85-90 degrees; one side surface of the first folded plate (3) is fixed on the inner wall of the fourth side wall (1-8), and a gap is reserved between the other side surface of the first folded plate (3) and the inner wall of the third side wall (1-7); one side surface of the second folded plate (4) is fixed on the inner wall of the third side wall (1-7), and a gap is reserved between the other side surface of the second folded plate (4) and the inner wall of the fourth side wall (1-8); one side surface of the third folded plate (5) is fixed on the inner wall of the fourth side wall (1-8), and a gap is reserved between the other side surface of the third folded plate (5) and the inner wall of the third side wall (1-7); a first medicine adding opening (1-3) and a second medicine adding opening (1-4) are respectively arranged at the upper part of the fourth side wall (1-8), the first medicine adding opening (1-3) and the second medicine adding opening (1-4) are equal in height, and the height is larger than that of the first folded plate (3); the first medicine adding opening (1-3) is arranged between the first side wall (1-5) and the first folded plate (3), and the second medicine adding opening (1-4) is arranged between the second folded plate (4) and the third folded plate (5); a third medicine adding opening (1-2) is formed in the upper portion of the third side wall (1-7), the third medicine adding opening (1-2) and the second medicine adding opening (1-4) are equal in height, and the third medicine adding opening (1-2) is formed between the second folded plate (4) and the first folded plate (3); a first water outlet is formed in the bottom of the second side wall (1-6) and is relatively close to the fourth side wall (1-8);
a negative plate (6) and an anode plate (7) are arranged inside the double-effect recovery tank (2), a direct-current power supply (8) is arranged outside the double-effect recovery tank (2), the negative electrode of the direct-current power supply (8) is connected with the negative plate (6), and the positive electrode of the direct-current power supply (8) is connected with the anode plate (7); the lower part of the side wall of the double-effect recovery tank (2) is provided with a second water inlet and a second water outlet (2-1), the second water inlet is communicated with the first water outlet of the oxidation de-complexing tank (1) through a water pipe (9), and the side wall where the second water inlet and the second water outlet (2-1) are located is two opposite side walls.
2. The use method of the device for pretreating complex heavy metals in electroplating cleaning wastewater by using the catalytic oxidation method according to claim 1, characterized in that the cathode plate (6) is a stainless steel plate.
3. The use method of the device for pretreating complex heavy metals in electroplating cleaning wastewater by using the catalytic oxidation method according to claim 1, characterized in that the anode plate (7) is an inert carbon electrode.
4. The use method of the device for pretreating complex heavy metals in electroplating cleaning wastewater by using the catalytic oxidation method according to claim 3, wherein the inert carbon electrode is a glassy carbon electrode or a graphite electrode.
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