CN112142166A - Three-dimensional porous NiO/NF active material, preparation method and application thereof, and device for removing heavy metal ions in wastewater by electrocoagulation method - Google Patents
Three-dimensional porous NiO/NF active material, preparation method and application thereof, and device for removing heavy metal ions in wastewater by electrocoagulation method Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 48
- 239000011149 active material Substances 0.000 title claims abstract description 43
- 150000002500 ions Chemical class 0.000 title claims abstract description 43
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000009297 electrocoagulation Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 142
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 14
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 12
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- SJHUQGQHKBUYQV-UHFFFAOYSA-L dichlorocadmium;dihydrate Chemical compound O.O.Cl[Cd]Cl SJHUQGQHKBUYQV-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- -1 electroplating Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a three-dimensional porous NiO/NF active material, a preparation method and application thereof, wherein the three-dimensional porous NiO/NF active material takes reticulated porous foam nickel NF as a structural framework, NiO nano sheets vertically grow on the surface of the foam nickel NF, and the NiO nano sheets are not stacked; when in preparation, the foamed nickel after acid treatment, the nickel acetate, the urea and the ammonium fluoride are added into a reaction kettle together, and then the reaction is carried out by sealing and heating to obtain Ni (OH)2/NF; mixing the obtained Ni (OH)2the/NF is obtained by high-temperature heating reaction in oxygen atmosphere, and the NiO/NF active material can be used as an anode. On the basis, the invention further provides a device for removing heavy metal ions in the wastewater by electrocoagulation, which can not only treat the wastewater discharged by industry in a fixed-point interception mode,and the intelligent robot treatment mode can be used for treating the water area polluted by the heavy metal ions, so that selective fixed-point treatment is realized.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a three-dimensional porous NiO/NF active material, a preparation method and application thereof, and a device for removing heavy metal ions in wastewater by an electrocoagulation method.
Background
In recent years, due to great development of industry, a large amount of industrial wastewater is generated, particularly in the electroplating and leather manufacturing industries, and a large amount of industrial wastewater containing heavy metal ions is generated. Heavy metal ions, as a pollutant, have extremely strong toxicity and carcinogenicity, and are almost harmful to various organs of the human body. In addition, the heavy metal ions are not easy to degrade and can be transferred and accumulated in a food chain and ingested by human beings, so that the heavy metal ions in the industrial wastewater are removed, the national specified discharge standard is reached, and the method is a key point of much attention of various related enterprises. The existing removal method for removing heavy metal ions comprises a chemical precipitation method, wherein a precipitator is added and the pH value is adjusted to precipitate and remove the heavy metal ions, but the method needs to add the precipitator or a trapping agent outside, can generate a large amount of sludge, is a disposable product, has higher cost and has the risk of introducing secondary pollution; the adsorption method is also a common method, and heavy metal ions in the wastewater are adsorbed and removed by an adsorbent, and the method is environment-friendly, but has weak environmental adaptation to a solution and long removal time; the membrane separation method takes a selective permeable membrane as a separation medium, when certain driving force exists on two sides of the membrane, components on the raw material side selectively permeate the membrane so as to achieve the purposes of separating and removing harmful components, and the method has the advantages of simple operation, simple device, high operation cost, low mechanical strength of the membrane and short service life; the catalytic reduction method utilizes electric energy or light energy to catalytically degrade heavy metal ions and reduce toxicity, but the prior art is still immature and has low efficiency. Therefore, the development of a method for removing heavy metal ions in industrial wastewater with high efficiency, environmental protection and low cost has great help and demand for related industrial enterprises.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
In order to overcome the defects of the method for removing heavy metal ions in various wastewater in the prior art, the invention aims to provide a three-dimensional porous NiO/NF active material, a preparation method and application thereof;
the second aspect of the invention aims to provide a device for removing heavy metal ions in wastewater by electrocoagulation.
In order to achieve the object of the first aspect of the present invention, the present invention provides the following technical solutions:
a three-dimensional porous NiO/NF active material takes reticulated porous foam nickel NF as a structural framework, NiO nano-sheets vertically grow on the surface of the foam nickel NF, and no stack exists between the NiO nano-sheets.
A preparation method of a three-dimensional porous NiO/NF active material comprises the following steps:
(1) foam nickel pretreatment: soaking the foamed nickel in concentrated hydrochloric acid until bubbles are generated, and then cleaning to be neutral and drying;
(2) preparation of Ni (OH)2/NF: weighing 2.000g to 2.588g (such as 2.2 g, 2.3 g, 2.4 g, 2.5g and the like) of nickel acetate, 2.500g to 4.000g (such as 2.7 g, 3.2g, 3.5g, 3.8g and the like) of urea and 0.700g to 0.78g (such as 0.72 g, 0.74 g, 0.75g and the like) of ammonium fluoride, adding deionized water, and stirring uniformly to obtain a mixed solution; taking a proper amount ofAdding the mixed solution and the foam nickel pretreated in the step (1) into a reaction kettle, sealing, preserving the temperature for 4-6 h (for example, 4.5, 5, 5.5h and the like) at the temperature of 120-150 ℃ (for example, 125, 130, 140, 145, 148 ℃ and the like), cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning to be neutral, and drying to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2Heating the/NF to 400-plus 500 ℃ (for example, 420, 450, 480 ℃ and the like) in an oxygen atmosphere, then preserving the heat for 2-4 h (for example, 2.5, 3.0, 3.5h and the like) at 400-plus 500 ℃, wherein the heating rate during heating is 1-3 ℃/min (for example, 1.5, 2.0, 2.5 ℃/min and the like), and obtaining the three-dimensional porous NiO/NF active material after the reaction is finished.
The preparation method of the three-dimensional porous NiO/NF active material preferably comprises the following steps:
(1) foam nickel pretreatment: soaking 2cm by 4cm of foamed nickel in concentrated hydrochloric acid until bubbles are generated, and then cleaning to be neutral and drying;
(2) preparation of Ni (OH)2/NF: weighing 2.000-2.588 g of nickel acetate, 2.500-4.000 g of urea and 0.700-0.78 g of ammonium fluoride, adding 100mL of deionized water, and uniformly stirring to obtain a mixed solution; adding 20mL of the mixed solution and the foam nickel pretreated in the step (1) into a reaction kettle, sealing, preserving the heat for 4-6 h at the temperature of 120-150 ℃ in a drying box, cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning to be neutral, and drying to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2Placing the NF in a tubular furnace, heating to 400-500 ℃ in an oxygen atmosphere, then preserving the heat for 2-4 h at the temperature of 400-500 ℃, wherein the heating rate is 1-3 ℃/min during heating, and obtaining the three-dimensional porous NiO/NF active material after the reaction is finished.
The preparation method of the three-dimensional porous NiO/NF active material preferably comprises the following steps:
(1) foam nickel pretreatment: cutting to 2 x 4cm2The foam nickel is pretreated, soaked in concentrated hydrochloric acid until bubbles are generated, and then ultrasonically cleaned by deionized waterWashing for 3 times until water is neutral, finally ultrasonically washing for 5min by using absolute ethyl alcohol, and then drying for 6h in a drying oven at 80 ℃;
(2) preparation of Ni (OH)2/NF: weighing 2.488g +/-0.1 g of nickel acetate, 3.000g +/-0.5 g of urea and 0.740g +/-0.02 g of ammonium fluoride, putting the materials into a beaker, adding 100mL of deionized water, and stirring for 30min to obtain the mixed solution; weighing 20mL of the mixed solution and the foam nickel pretreated in the step (1), putting the mixed solution and the foam nickel in a 40mL stainless steel reaction kettle, sealing, and keeping the temperature in a drying oven at 120 ℃ for 6 hours; cooling to room temperature, taking out the foamed nickel, washing with deionized water and anhydrous ethanol for 3 times, and drying in a drying oven at 80 deg.C for 6h to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2and/NF keeping the temperature in the tube furnace at 400 ℃ for 3h under the oxygen atmosphere, wherein the heating rate is 3 ℃/min, and the three-dimensional porous NiO/NF active material is obtained.
The three-dimensional porous NiO/NF active material or the three-dimensional porous NiO/NF active material prepared by the preparation method of the three-dimensional porous NiO/NF active material is applied to removing heavy metal ions in wastewater by an electrocoagulation method, and when the three-dimensional porous NiO/NF active material is applied, the three-dimensional porous NiO/NF active material is used as an anode.
In order to achieve the object of the second aspect of the present invention, the present invention provides the following technical solutions:
an apparatus for removing heavy metal ions from wastewater by electrocoagulation, comprising:
connecting an external power supply;
anode: is made of three-dimensional porous NiO/NF active material;
cathode: a graphite plate;
the anode is connected with the anode of the external power supply, and the cathode is connected with the cathode of the external power supply;
blocking: and enclosing the periphery and the bottom end of the electrocoagulation region formed by the anode and the cathode to collect precipitates generated by electrocoagulation.
The device for removing heavy metal ions in wastewater by electrocoagulation as described above preferably further comprises a water quality detection device for detecting the water quality condition of the peripheral area of the electrode.
The device for removing heavy metal ions in wastewater by electrocoagulation as described above is preferably placed in a wastewater treatment tank for use.
The device for removing heavy metal ions in wastewater by electrocoagulation as described above is preferably mounted on a ship or an underwater robot and operates along with the ship or the underwater robot.
According to the device for removing heavy metal ions in wastewater by the electrocoagulation method, the applied voltage of the external power supply is 0.2-1.5V.
Compared with the closest prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) according to the defects of various methods for treating heavy metal ions in industrial wastewater at present, the invention provides the three-dimensional porous NiO/NF active material, the active material is used as an anode for removing the heavy metal ions in the wastewater, and the three-dimensional porous NiO/NF active material is efficient, environment-friendly, low in cost and simple and convenient to operate. When the method is used, a large amount of flocculating agents can be generated in situ only by applying an external electric field on the prepared active electrode, heavy metal ions in wastewater are complexed, the highly toxic heavy metal ions can be reduced on the cathode, the pH value of the solution can be gradually increased along with the removal process, so that the solution is precipitated, and no reducing agent is added and the pH value is adjusted.
(2) On the basis of the three-dimensional porous NiO/NF active material, the invention can realize timely recovery and intelligent maneuvering transfer of sludge by designing a treatment device for removing heavy metal ions in wastewater by an electrocoagulation method. When in use, the device is combined with an underwater robot or a ship, is applied to a water area polluted by heavy metal, and is used for fixed-point treatment. Install the block around active electrode, the mud of production can in time be recycled by the recovery processing, prevents to get into the water and causes the pollution, has reduced the cost of follow-up processing to through real-time detection quality of water, when it reaches the operation standard, then transfer underwater robot or steamer to next heavy concentration region through remote control technique and get rid of, realized processing apparatus's flexible, improved the practicality. The active material and the treatment device have strong applicability, wide applicable range of solution pH and coexisting heavy metal ions, and good application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a tubular furnace pyrolysis three-dimensional Ni (OH) according to an embodiment of the present invention2a/NF state diagram;
FIG. 2 is SEM images (panels b and c) of foamed nickel NF (panel a) and NiO/NF of an example of the present invention;
FIG. 3 is a diagram of an experimental apparatus for removing Cr (VI) in an embodiment of the present invention;
FIG. 4 shows the removal rates of Cr, Cu, Fe, Zn and Cd in the examples of the present invention;
FIG. 5 is a diagram illustrating a fixed point interception mode according to an embodiment of the present invention;
fig. 6 is a schematic diagram of a processing mode of the intelligent robot according to the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are for convenience of description of the present invention only and do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. The terms "connected" and "connected" used herein should be interpreted broadly, and may include, for example, a fixed connection or a detachable connection; they may be directly connected or indirectly connected through intermediate members, and specific meanings of the above terms will be understood by those skilled in the art as appropriate.
The invention provides a method for efficiently removing heavy metal ions in industrial wastewater by using a three-dimensional porous NiO/NF as an active electrode through electrocoagulation, and two practical application treatment devices are designed, which can be divided into 1) a fixed-point interception treatment mode; 2) intelligent robot handling mode. This processing apparatus set electrolysis, flocculation, deposit, mud is retrieved, water quality testing, and multiple step is shifted in the remote control, can in time retrieve the mud that produces, prevent that it from getting into the water and causing the pollution, reduced the produced mud subsequent processing's of present processing waste water cost, improved processing apparatus's flexible flexibility and intellectuality, not only can use the fixed point interception mode to handle the waste water that the industry discharged, can also utilize intelligent robot to handle the water territory that heavy metal ion pollutes, realize selectivity fixed point and handle.
As a first aspect of the invention, a three-dimensional porous NiO/NF active material is provided, wherein a reticulated porous foam nickel NF is used as a structural skeleton, NiO nano-sheets vertically grow on the surface of the reticulated porous foam nickel NF, and no stack exists between the NiO nano-sheets. In the invention, the active material takes the reticulated porous Nickel Foam (NF) as a substrate, so that a large surface area is provided for the vertical growth of the NiO nano-sheets, the three-dimensional porous structure of the nickel foam is beneficial to the flow of liquid, the nickel foam is a preferable electrode substrate material, the NiO nano-sheets vertically grow on the surface of the nickel foam, the stacking of the nano-sheets is avoided, and more active sites can be exposed. The preparation process of the three-dimensional porous active material NiO/NF comprises the following steps:
cutting to 2 x 4cm2The foam nickel is pretreated, is soaked in concentrated hydrochloric acid until bubbles are generated, is ultrasonically cleaned for 3 times by deionized water until the water is neutral, is ultrasonically cleaned for 5min by absolute ethyl alcohol, and is then placed in a drying box to be dried for 6h at the temperature of 80 ℃; and (5) weighing 2.488g +/-0.1 g (namely 2.388-2.588g) of nickel acetate, 3.000g +/-0.5 g (namely 2.5-3.5g) of urea and 0.740g +/-0.02 g of ammonium fluoride (namely 0.72-0.76g) are put into a beaker, 100mL of deionized water is added, and the mixture is stirred for 30min to obtain a mixed solution; measuring 20mL of the mixed solution and the pretreated nickel foam, putting the mixed solution and the pretreated nickel foam into a 40mL stainless steel reaction kettle, sealing, and preserving heat for 6 hours at 120 ℃ in a drying oven; cooling to room temperature, taking out the foamed nickel, washing with deionized water and anhydrous ethanol for 3 times, and drying in a drying oven at 80 deg.C for 6h to obtain Ni (OH)2/NF; then, adding Ni (OH)2and/NF keeping the temperature in the tube furnace at 400 ℃ for 3h under the oxygen atmosphere, wherein the heating rate is 3 ℃/min, and obtaining the three-dimensional porous NiO/NF active electrode.
The three-dimensional porous NiO/NF active electrode prepared by the method is taken as an anode to remove heavy metal ions in wastewater by an electrocoagulation method, and specifically comprises the following steps:
the NiO/NF active electrode is used as an anode, an anode of an external power supply and a graphite plate are used as a cathode, a cathode of the external power supply are applied with a voltage of 0.2-1.5V and stirred, and a flocculating agent generated by anode electrolysis can efficiently remove suspended matters and heavy metal ions such as chromium, zinc, iron, copper, cadmium and the like in water through complexing precipitation, so that sludge is finally formed and separated to achieve the purpose of treatment.
As a second aspect of the invention, the practical treatment device for removing heavy metal ions in wastewater by electrocoagulation is based on the NiO/NF active electrode and combines practical situations to design the following two treatment modes:
1) fixed point interception processing mode
The mode can be applied to factories for producing heavy metal wastewater such as electroplating, leather manufacturing, dye and the like, a sewage treatment tank is built at the adjacent position of the sewage treatment tank, the wastewater is injected from a water inlet of the treatment tank, a water outlet is sealed, the NiO/NF active electrode and the graphite sheet are respectively used as an anode and a cathode to be placed in the wastewater, the NiO/NF active electrode and the graphite sheet are respectively connected with the anode and the cathode of a power supply, a blocking device is designed around the electrode to filter the generated sludge and prevent the sludge from entering a water body; after the flocculation and precipitation, the water quality is detected in real time through a heavy metal ion detector, when the water quality meets the water use standard, a water outlet is opened, a treatment pool is removed, and the electrodes and the blocking device are detachable and can be replaced and cleaned regularly.
2) Intelligent robot handling mode
This mode can be applied to areas heavily contaminated with heavy metals. The NiO/NF and the graphite are respectively used as an anode and a cathode and are arranged at the bottom of the ship, a power supply is arranged in the ship, and a barrier net is arranged around the electrode and is used for filtering sludge. The nickel hydroxide flocculating agent generated by the anode electrolysis can complex and precipitate heavy metal ions in water, and the heavy metal ions are filtered and recovered by the blocking net, so that the heavy metal ions are prevented from entering a water body to cause pollution, and the cost of subsequent treatment is saved. And through real-time detection of water quality, when the water quality reaches the use standard, the water quality is moved to the next highly polluted water area through remote control to be removed.
Example 1
A NiO/NF active material with a three-dimensional porous structure can be directly used as an active electrode anode for removing heavy metal ions in industrial wastewater through electrocoagulation, and is prepared by the following steps:
s11, pretreatment nickel foam: placing 40mm by 20mm by 1.5mm cut foam nickel in a 100mL beaker, measuring 20mL of concentrated hydrochloric acid by using a 100mL measuring cylinder, adding the concentrated hydrochloric acid into the beaker, immersing the foam nickel, standing for 5min, observing that bubbles are generated on the surface of the foam nickel, taking out the foam nickel, washing the foam nickel for 3 times by using deionized water, washing the foam nickel for 3 times by using absolute ethyl alcohol, sucking the ethyl alcohol on the surface by using filter paper, inclining the foam nickel in the beaker, and drying the foam nickel for 6h at the temperature of 80 ℃ in a drying box;
s12 preparation of Ni (OH)2/NF: weighing 2.5g of nickel acetate, 0.7g of ammonium fluoride and 3.2g of urea, placing the materials in a 100mL beaker, weighing 100mL of deionized water by using a 100mL measuring cylinder, pouring the deionized water into the beaker, and magnetically stirring for 20min to obtain a mixed solution; placing the dried foamed nickel obtained in the step s11 into a 40mL stainless steel reaction kettle lining, measuring 17mL of the mixed solution by using a 50mL measuring cylinder, mixing the mixed solution with the foamed nickel, sealing, standing for 2h, placing the mixture into a drying oven, keeping the temperature at 120 ℃ for 6h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times in sequence, and drying in the drying oven at 80 ℃ for 6h to obtain Ni (OH)2/NF；
s13 reaction of Ni (OH) obtained in s122Annealing of NF in a tube furnace: wiping a furnace pipe of the high-temperature tubular furnace with deionized water, wiping with absolute ethyl alcohol, and airing to ensure that the inside of the pipe is clean; drying Ni (OH)2the/NF is lightly put on a corundum crucible with the thickness of 50mm 20mm, then the corundum crucible is lightly pushed into the middle of a furnace tube, a flange is sealed, oxygen is vacuumized and cleaned for 3 times, the furnace tube is pumped to 2E-02Torr each time, then oxygen is introduced to the atmospheric pressure of 6.9E02 Torr, the air in the tube is removed, the tube is put into a high-temperature tube furnace to be insulated for 3 hours at the temperature of 400 ℃, the heating rate is 3 ℃/min, and the generated NiO/NF is taken out to be packaged and stored after being naturally cooled to the room temperature.
s14, product storage: the prepared NiO/NF with the three-dimensional hierarchical pore structure is stored in a sample bag and is stored in a sealed way, and the NiO/NF needs to be moisture-proof, sun-proof and acid, alkali and salt corrosion resistant, and has the storage temperature of 20 ℃ and the relative humidity of 10 percent.
FIG. 1 shows a tubular furnace pyrolysis three-dimensional porous Ni (OH)2The method is characterized in that the/NF prepares a state diagram of the multi-level pore structure NiO/NF, and the positions and the connection relations of all parts are correct and operate in sequence. Ni (OH)2The thermal decomposition of/NF was carried out in a high temperature tube furnace and was carried out in an oxygen atmosphere in a heated state.
The invention further uses a scanning electron microscope to perform morphology and structure analysis on the NiO/NF active material prepared in example 1, as shown in fig. 2a, macroscopic and microscopic (inset) morphology graphs of Nickel Foam (NF) are shown, which shows a three-dimensional reticular porous structure thereof, and provides a large surface area for the growth of NiO. Fig. 2b and c show a macro-image (fig. 2b) and a micro-topography (fig. 2c) of NiO/NF, and it can be seen that a large number of NiO nano-sheets grow vertically on the surface of the foam nickel structural skeleton, so that a large number of pore structures are formed, and a large number of active sites are exposed in the structures.
The three-dimensional porous active electrode NiO/NF is used as an anode to remove heavy metal ions in an aqueous solution, and the specific process is as follows:
s21, potassium dichromate as chromium source, used to simulate chromium containing wastewater: firstly, placing about 20 +/-1 g of potassium dichromate in a 50mL beaker, drying for 2h at 110 ℃ in a drying oven, then weighing 0.2829 +/-0.0001 g of dried potassium dichromate in a 100mL beaker, pouring a proper amount of water to dissolve the potassium dichromate, transferring the potassium dichromate to a 1000mL volumetric flask, adding water to dilute the potassium dichromate to a scale mark, namely preparing 100mg/L hexavalent chromium stock solution, and then obtaining the hexavalent chromium stock solution with other concentrations through diluting the solution stock solution;
s22, taking 20mL of storage solution into a 100mL beaker by using a 100mL measuring cylinder, then taking 80mL of deionized water to dilute into 20mg/L hexavalent chromium solution, taking 30 μ L of 1:1 hydrochloric acid by using a liquid-transferring gun, adding the hydrochloric acid into the solution, adjusting the pH to 5, weighing 0.5844 +/-0.01 g of sodium chloride, adding the sodium chloride into the beaker, and magnetically stirring for 20min to obtain simulated Cr waste liquid;
s23, as shown in FIG. 3, using the NiO/NF active material prepared in example 1 as an anode, a graphite sheet as a cathode, and clamped by a commercial platinum electrode clamp, a calomel electrode as a reference electrode, an electrochemical workstation as a power supply to supply energy, and applying a voltage of 0.5V while stirring for removal;
s24, processing for 20min, centrifuging the solution at 10000r/min, taking the supernatant, and measuring the concentration of hexavalent chromium in the supernatant by adopting a diphenylcarbonyldihydrazide spectrophotometry, wherein the concentration of the hexavalent chromium is reduced from 20mg/L to 0.08 mg/L.
Following a procedure substantially identical to the above-described application test, with the difference that: changing the voltage of the electrochemical workstation in the step s23 to 1V, and treating for 10 min; then the solution is centrifuged and detected, and the concentration of hexavalent chromium is reduced from 20mg/L to 0.08 +/-0.02 mg/L.
Application test three
Following a procedure substantially identical to the above-described application test, with the difference that: replacing the electrochemical workstation in the step s23 with a commercial 1.5V first battery, and processing for 40 min; then the solution is centrifuged and detected, and the concentration of hexavalent chromium is reduced from 20mg/L to 0.08 +/-0.02 mg/L.
Application test four
Following a procedure substantially identical to the above-described application test, with the difference that: replacing the simulated Cr waste liquid in the step s22 with the following solutions: measuring 50mL of hexavalent chromium storage solution by using a 100mL measuring cylinder, pouring the hexavalent chromium storage solution into a 100mL beaker, measuring 50mL of deionized water by using the 100mL measuring cylinder to dilute the hexavalent chromium storage solution into 50mg/L Cr solution, weighing 22.74mg of zinc nitrate hexahydrate, 36.17mg of ferric nitrate nonahydrate, 13.4mg of copper chloride dihydrate, 10.16mg of cadmium chloride dihydrate and 0.5844 +/-0.01 g of sodium chloride, adding the hydrochloric acid of 30 mu L1: 1 into the Cr solution by using a pipetting gun, adjusting the pH value to be 5, and magnetically stirring for 20min to obtain simulated Cr waste liquid used in the application test IV; and the application tests are four, and the treatment time is 30 min; after treatment, the solution was centrifuged, and the concentration was measured by inductively coupled plasma, as shown in fig. 4, the removal rates of chromium, copper, iron, zinc, and cadmium were 99.85%, 99.97%, 99.98%, 99.88%, and 99.56%, respectively.
The operation of this comparative experiment 1 is essentially the same as the application experiment one, except that: the applied voltage in step s23 was changed to 0.1V.
And centrifuging and detecting the solution after 20min treatment, wherein the concentration of hexavalent chromium is only reduced to 2 +/-0.1 mg/L from 20mg/L, and the hexavalent chromium does not reach the use standard.
This comparative run 2 was essentially identical to the operation of example 1 and application run one, except that: the oxygen atmosphere in step s13 was changed to an argon atmosphere.
And centrifuging and detecting the solution after 20min treatment, wherein the concentration of hexavalent chromium is only reduced to 1 +/-0.1 mg/L from 20mg/L, and the hexavalent chromium does not reach the use standard.
Example 2: fixed point interception processing mode
The treatment mode is suitable for fixing places where heavy metal-containing wastewater is generated, such as electroplating plants, leather manufacturing plants, machining places and the like. As shown in fig. 5, the NiO/NF active electrode is connected with the positive electrode of the external power supply, the graphite flake is connected with the negative electrode of the external power supply, a blocking net is arranged around the electrode, wastewater enters the treatment tank from the water inlet above, the power supply is turned on, the anode starts to electrolyze to generate a flocculating agent, heavy metal ions are subjected to complexing precipitation, generated sludge is filtered by the blocking net and is timely recovered, the water quality is detected in real time through a water quality detection device, the water outlet is opened to meet the water use standard, water is discharged, wastewater is injected again, and the process is circulated. Wherein, electrode and block all are detachable design, can change regularly.
Example 3: intelligent robot handling mode
This mode of treatment is suitable for treating areas heavily contaminated with heavy metals. As shown in figure 6, the electrode is arranged at the bottom of the ship, the power supply is arranged in the ship, the blocking net is arranged around the electrode, when the ship drives into a certain heavily polluted water area, the power supply is turned on to be removed, the generated sludge is filtered and recovered by the blocking net to avoid entering the water body, the water quality is monitored in real time, and when the water quality reaches the water use standard, the ship can be driven to be transferred to another heavily polluted water area, so that selective fixed-point treatment is realized, and the ship has high maneuvering flexibility.
The treatment device integrates multiple steps of electrolysis, flocculation, sedimentation, sludge recovery, water quality detection and remote control transfer, can timely recover the generated sludge, prevent the sludge from entering a water body to cause pollution, improve the maneuvering flexibility and the intellectualization of the treatment device, not only can treat the industrial discharged wastewater by using a fixed-point interception mode, but also can treat a water area polluted by heavy metal ions by using an intelligent robot treatment mode, realize selective fixed-point treatment, reduce the cost of subsequent treatment of the sludge generated by the current wastewater treatment, and improve the maneuvering flexibility of the treatment device.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. The three-dimensional porous NiO/NF active material is characterized in that reticulated porous foam nickel NF is used as a structural framework, NiO nano sheets vertically grow on the surface of the foam nickel NF, and the NiO nano sheets are not stacked.
2. A preparation method of a three-dimensional porous NiO/NF active material is characterized by comprising the following steps:
(1) foam nickel pretreatment: soaking the foamed nickel in concentrated hydrochloric acid until bubbles are generated, and then cleaning to be neutral and drying;
(2) preparation of Ni (OH)2/NF: weighing 2.000-2.588 g of nickel acetate, 2.500-4.000 g of urea and 0.700-0.78 g of ammonium fluoride, adding deionized water, and uniformly stirring to obtain a mixed solution; adding a proper amount of the mixed solution and the foam nickel pretreated in the step (1) into a reaction kettle, sealing and preserving heat for 4-6 h at the temperature of 120-150 ℃, cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning to be neutral and drying to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2Heating NF to 400-plus-500 ℃ in an oxygen atmosphere, then preserving heat for 2-4 h at 400-plus-500 ℃, wherein the heating rate is 1-3 ℃/min during heating, and obtaining the three-dimensional porous NiO/NF active material after the reaction is finished.
3. The method of preparing the three-dimensional porous NiO/NF active material of claim 2, comprising the steps of:
(1) foam nickel pretreatment: soaking 2cm by 4cm of foamed nickel in concentrated hydrochloric acid until bubbles are generated, and then cleaning to be neutral and drying;
(2) preparation of Ni (OH)2/NF: weighing 2.000-2.588 g of nickel acetate, 2.500-4.000 g of urea and 0.700-0.78 g of ammonium fluoride, adding 100mL of deionized water, and uniformly stirring to obtain a mixed solution; adding 20mL of the mixed solution and the foam nickel pretreated in the step (1) into a reaction kettle, sealing, preserving the heat for 4-6 h at the temperature of 120-150 ℃ in a drying box, cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning to be neutral, and drying to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2Placing the NF in a tubular furnace, heating to 400-500 ℃ in an oxygen atmosphere, then preserving the heat for 2-4 h at the temperature of 400-500 ℃, wherein the heating rate is 1-3 ℃/min during heating, and obtaining the three-dimensional porous NiO/NF active material after the reaction is finished.
4. The method of preparing the three-dimensional porous NiO/NF active material of claim 3, comprising the steps of:
(1) foam nickel pretreatment: cutting to 2 x 4cm2The foam nickel is pretreated, is soaked in concentrated hydrochloric acid until bubbles are generated, is ultrasonically cleaned for 3 times by deionized water until the water is neutral, is ultrasonically cleaned for 5min by absolute ethyl alcohol, and is then placed in a drying box to be dried for 6h at the temperature of 80 ℃;
(2) preparation of Ni (OH)2/NF: weighing 2.488g +/-0.1 g of nickel acetate, 3.000g +/-0.5 g of urea and 0.740g +/-0.02 g of ammonium fluoride, putting the materials into a beaker, adding 100mL of deionized water, and stirring for 30min to obtain the mixed solution; weighing 20mL of the mixed solution and the foam nickel pretreated in the step (1), putting the mixed solution and the foam nickel in a 40mL stainless steel reaction kettle, sealing, and keeping the temperature in a drying oven at 120 ℃ for 6 hours; cooling to room temperature, taking out the foamed nickel, washing with deionized water and anhydrous ethanol for 3 times, and drying in a drying oven at 80 deg.C for 6h to obtain Ni (OH)2/NF；
(3) Preparing NiO/NF: mixing the Ni (OH) obtained in the step (2)2and/NF keeping the temperature in the tube furnace at 400 ℃ for 3h under the oxygen atmosphere, wherein the heating rate is 3 ℃/min, and the three-dimensional porous NiO/NF active material is obtained.
5. The use of the three-dimensional porous NiO/NF active material of claim 1 or the three-dimensional porous NiO/NF active material prepared by the method for preparing the three-dimensional porous NiO/NF active material of any one of claims 2to 4 in the removal of heavy metal ions in wastewater by electrocoagulation, wherein: the three-dimensional porous NiO/NF active material is used as an anode.
6. An apparatus for removing heavy metal ions from wastewater by electrocoagulation, comprising:
connecting an external power supply;
anode: is made of three-dimensional porous NiO/NF active material;
cathode: a graphite plate;
the anode is connected with the anode of the external power supply, and the cathode is connected with the cathode of the external power supply;
blocking: and enclosing the periphery and the bottom end of the electrocoagulation region formed by the anode and the cathode to collect precipitates generated by electrocoagulation.
7. The electrocoagulation apparatus of claim 6, further comprising water quality detection means for detecting water quality in the region surrounding the electrodes.
8. The electrocoagulation apparatus of claim 7, wherein the apparatus is used in a wastewater treatment tank.
9. The electrocoagulation apparatus of claim 7, wherein the apparatus is mounted on a ship or underwater robot and moves with the ship or underwater robot.
10. The electrocoagulation apparatus of any one of claims 6 to 9, wherein the external power supply applies a voltage of 0.2 to 1.5V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113721635A (en) * | 2021-09-14 | 2021-11-30 | 江苏理工学院 | Photoelectrochemistry chlorine salt removing underwater robot |
| CN114574895A (en) * | 2022-03-18 | 2022-06-03 | 南京师范大学 | Foam nickel loaded Ru-NiO hydrogen evolution reaction catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090065442A1 (en) * | 2007-03-12 | 2009-03-12 | C-Tech Industries, Inc. | Wastewater treatment and recycling system |
| CN203639210U (en) * | 2014-01-13 | 2014-06-11 | 中国水电顾问集团中南勘测设计研究院有限公司 | Simple electrochemical reaction device and electrochemical reaction tank |
| CN106186212A (en) * | 2016-09-14 | 2016-12-07 | 霍普科技（天津）股份有限公司 | A kind of electricity flocculation sewage treatment pot |
| CN109225123A (en) * | 2018-10-18 | 2019-01-18 | 太原理工大学 | It is a kind of using three-dimensional foam nickel as the preparation method and application of the hierarchical porous structure NiO/Ni of skeleton |
| CN110683715A (en) * | 2019-10-30 | 2020-01-14 | 徐州工程学院 | Rural domestic sewage recycling classification high-efficiency treatment system |
-
2020
- 2020-08-14 CN CN202010820195.XA patent/CN112142166A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090065442A1 (en) * | 2007-03-12 | 2009-03-12 | C-Tech Industries, Inc. | Wastewater treatment and recycling system |
| CN203639210U (en) * | 2014-01-13 | 2014-06-11 | 中国水电顾问集团中南勘测设计研究院有限公司 | Simple electrochemical reaction device and electrochemical reaction tank |
| CN106186212A (en) * | 2016-09-14 | 2016-12-07 | 霍普科技（天津）股份有限公司 | A kind of electricity flocculation sewage treatment pot |
| CN109225123A (en) * | 2018-10-18 | 2019-01-18 | 太原理工大学 | It is a kind of using three-dimensional foam nickel as the preparation method and application of the hierarchical porous structure NiO/Ni of skeleton |
| CN110683715A (en) * | 2019-10-30 | 2020-01-14 | 徐州工程学院 | Rural domestic sewage recycling classification high-efficiency treatment system |
Non-Patent Citations (3)
| Title |
|---|
| WANG ZHIFEI ET AL.: ""Annealing temperature effect on 3D hierarchically porous NiO/Ni for removal of trace hexavalent chromium"", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| ZHIFEI WANG ET AL.: ""3D hierarchically porous NiO/NF electrode for the removal of chromium(VI) from wastewater by electrocoagulation"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 董晓丹 等: ""用电凝聚装置去除废水中重金属离子"", 《安全与环境学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113721635A (en) * | 2021-09-14 | 2021-11-30 | 江苏理工学院 | Photoelectrochemistry chlorine salt removing underwater robot |
| CN114574895A (en) * | 2022-03-18 | 2022-06-03 | 南京师范大学 | Foam nickel loaded Ru-NiO hydrogen evolution reaction catalyst and preparation method thereof |
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