CN112371718A - Cd restoration based on graphite auxiliary primary battery2+Method for contaminating a medium - Google Patents

Cd restoration based on graphite auxiliary primary battery2+Method for contaminating a medium Download PDF

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Publication number
CN112371718A
CN112371718A CN202011138686.2A CN202011138686A CN112371718A CN 112371718 A CN112371718 A CN 112371718A CN 202011138686 A CN202011138686 A CN 202011138686A CN 112371718 A CN112371718 A CN 112371718A
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CN
China
Prior art keywords
medium
graphite
contaminating
polluted
copper plate
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Pending
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CN202011138686.2A
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Chinese (zh)
Inventor
吴正岩
陈超文
蔡冬清
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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Priority to CN202011138686.2A priority Critical patent/CN112371718A/en
Publication of CN112371718A publication Critical patent/CN112371718A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • 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
    • C02F1/46176—Galvanic cells
    • 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

Abstract

The invention discloses a method for repairing Cd based on graphite auxiliary primary battery2+The invention relates to a method for polluting a medium, which relates to the technical field of primary batteries and comprises the following steps: (1) pretreatment of a polluted medium: adding graphite powder into the surface layer of the polluted medium; (2) wrapping the surfaces of the zinc plate and the copper plate with cotton cloth, and inserting Cd into the copper plate2+In a contaminated medium; (3) the zinc plate and the copper plate are connected through a copper wire, and the electrode reaction is maintained for more than 2 days. The invention has the beneficial effects that: after graphite powder is added, the electrical parameters of the primary battery are detected at different time periods, the output current of the battery can be obviously improved by adding the graphite powder on the surface, the output power of the battery is 0.2-25mW, and Cd in the treated polluted medium is measured2+Concentration, graphite powder can effectively promote Cd in medium2+Removing, removingThe rate can reach more than 60%.

Description

Cd restoration based on graphite auxiliary primary battery2+Method for contaminating a medium
Technical Field
The invention relates to the technical field of primary batteries, in particular to a method for repairing Cd based on graphite auxiliary primary battery2+A method of contaminating a medium.
Background
With the development of modern industry, a large amount of heavy metal waste is discharged into the environmentCan cause serious water and soil pollution. Wherein Cd2+It is of great interest to researchers because of its high biotoxicity and its easy entry into the human body through the food chain. Thus, development techniques to repair Cd2+Polluted water and soil become a research hotspot in the current environmental field.
In the field of heavy metal pollution treatment, the traditional electrochemical restoration technology is simple to operate and removes Cd2+High efficiency and wide application. For example, patent publication No. CN 103936105a discloses an electrochemical method for treating industrial wastewater, which uses magnesium or magnesium alloy as an anode to effectively remove heavy metal elements in industrial wastewater. After the wastewater enters the electrochemical device, the high-activity magnesium hydroxide generated by the magnesium anode under the electrochemical action can efficiently adsorb heavy metal ions in the wastewater. However, the repairing method in the prior art consumes a large amount of electric energy, is easy to change the pH value of the environment, and is not beneficial to large-scale popularization.
Therefore, the development of a novel environment-friendly and low-energy-consumption Cd removal method is urgently needed2+Provided is a technique. For example, patent application with publication number CN110510709A discloses a removable Cd2+And its application, but Cd in the prior art2+The removal efficiency of (2) is low.
Disclosure of Invention
The technical problem to be solved by the invention is to remove Cd in the prior art2+The method has low removal efficiency, and provides a graphite-based auxiliary primary battery for restoring Cd2+A method of contaminating a medium.
The invention solves the technical problems through the following technical means:
cd restoration based on graphite auxiliary primary battery2+A method of contaminating a medium, comprising the steps of:
(1) pretreatment of a polluted medium: adding micron and/or nanometer level graphite powder into the polluted medium;
(2) coating the surfaces of the zinc plate and the copper plate with an isolating medium and then inserting Cd2+In a contaminated medium;
(3) the zinc plate and the copper plate are connected through a copper wire, and the electrode reaction is maintained for more than 2 days.
The working principle is as follows: the electrostatic induction effect of graphite in the built-in electric field of the battery is utilized to cause the field intensity near the graphite to be enhanced, so that the ion movement speed is accelerated, and the Cd is increased2+Removing efficiency and increasing output current.
Has the advantages that: after micron or nanometer level graphite powder is added, the graphite is flaky and has extremely small thickness (micron or nanometer level), and can float on the surface layer of a polluted medium; the electrical parameters of the primary battery are detected at different time periods, the output current of the battery can be obviously improved by adding the graphite powder on the surface, the output power is 0.2-25mW, and meanwhile, Cd in the treated polluted medium is measured2+Concentration, graphite powder can effectively promote Cd in medium2+The removal rate can reach more than 60 percent.
If the graphite powder with larger size is selected instead of micro-nano scale, the two ends of the graphite are not sharp enough, the density of induced charges generated at the two ends of the graphite is not enough under the action of an electric field in the battery, the field intensity nearby is increased lower, and Cd removal is realized2+The efficiency improvement effect is not obvious.
In order to prevent direct connection of the zinc plate, the copper plate and the graphite and reduce the current in the output circuit of the primary battery, the surfaces of the zinc plate and the copper plate are coated with an isolation medium to isolate the graphite.
Preferably, the isolation medium is cotton cloth.
Preferably, the mass fraction of the graphite powder in the polluted medium is 0.2-10%.
Has the advantages that: in the recording range of the invention, the higher the graphite powder addition, the higher the Cd2+The higher the removal rate. If the addition of graphite powder is lower than the recorded range, Cd is relative to the original battery without graphite2+The removal efficiency is not obviously improved, and if the adding amount of the graphite powder is higher than the recorded range, Cd2+The removal efficiency tends to be stable, and the lifting space is not large.
Preferably, the contaminated medium is water.
Has the advantages that: when the polluted medium is water, the graphite ash floats on the surface layer of the water due to the surface tension effect of the water.
Preferably, the polluted medium is soil, and potassium chloride is added into the soil, wherein the addition amount of the potassium chloride is 0.01-1.6% of the mass of the soil.
Preferably, the zinc plate is rectangular, and the surface area of the zinc plate is 2-100m2。
Preferably, the copper plate is rectangular, and the surface area of the copper plate is 2-100m2。
Preferably, the insertion depth of the zinc plate is 1-30cm, the insertion depth of the copper plate is 1-30cm, and the distance between the zinc plate and the copper plate is 2-150 cm.
Preferably, the electrode reaction is maintained for 2 to 10 days in the step (3).
The working principle of the invention is as follows: the invention is in Cd2+In the polluted medium, a zinc plate is used as an anode, a copper plate is used as a cathode and inserted into the polluted medium, the zinc plate and the copper plate are connected by a copper wire, spontaneous redox reaction in the system is used as an energy source of the primary battery, and graphite positioned on the surface layer of the polluted medium in a built-in electric field of the battery can cause the electric field intensity of the surface layer to be enhanced and attract Cd2+Migrating to the surface layer. Thus, under the action of the electric field, Cd2+Can move to the carbon rod along the surface layer and contact with the OH generated nearby-Reaction to Cd (OH)2And (4) precipitating.
The invention has the advantages that: compared with the primary battery in the prior art, the graphite-assisted primary battery can effectively enhance the surface layer ion concentration due to the addition of graphite in the polluted medium, the output current of the primary battery added with graphite is higher than that of the primary battery without graphite, and the output current of the battery and Cd2+The removal efficiency is further improved. The method can realize Cd2+And certain electric energy is output to the outside while the removal is carried out quickly, so that the application prospect is wide.
Compared with a primary battery without graphite, the Cd can be effectively improved after the graphite is added2+The removal efficiency is that the graphite on the surface layer of the polluted medium in the battery can cause the electric field intensity of the surface layer to be enhanced and attract Cd2+Migrate to the surface layer, so that the addition of graphite can realize the deep Cd of the medium2+Extracting.
The primary battery adopts the copper sheet as the cathode, can increase the electrochemical reaction area and enhance the hardness of the cathode, and is not easy to crack.
Drawings
FIG. 1 is an SEM image of graphite in the present invention;
FIG. 2 is a comparison of output currents of primary cells in comparative example 1 and example 2 according to the present invention;
FIG. 3 shows Cd in comparative example 1 and example 2 of the present invention2+The efficiency comparison results were removed.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
Cd restoration based on graphite auxiliary primary battery2+A method of contaminating a medium, comprising the steps of:
(1) pretreatment of a polluted medium: passing through a 10-mesh sieve to Cd2+Adding a mixture of micron-level graphite powder and nano-level graphite powder with the mass fraction of 0.2% into a polluted medium (water body or soil), wherein graphite can float on the surface of the medium; for Cd2+0.01 percent (mass fraction) of potassium chloride is added into the polluted soil and the polluted soil is mixed evenly; FIG. 1 is an SEM image of graphite; the graphite powder purchased in the embodiment contains micron-scale and nano-scale graphite powder;
(2) the surface area is 2cm2Has a rectangular zinc plate and a surface area of 2cm2Is rectangularThe surface of the copper plate is coated with a layer of medium and then vertically inserted with Cd from the upper part2+The depth of insertion in a polluted medium (water body or soil) is 1cm, and the distance between electrodes (a zinc plate and a copper plate) is 2 cm;
(3) the zinc plate and the copper plate were connected by a copper wire, and the electrode reaction was maintained for 2 days.
The electrical parameter detection is carried out on the primary battery at the initial moment, which shows that the addition of the graphite can obviously improve the output current of the battery, and the output power of the battery is 0.2 mW. Simultaneously, ICP-OES (inductively coupled plasma emission spectrometer) is adopted to respectively measure Cd in the polluted soil or the polluted water after 2 days of treatment2+The concentration of the obtained graphite can effectively promote Cd in the medium2+Removal of Cd from the polluted water2+The removal rate can reach 70 percent, and the removal rate of the polluted soil can reach 64 percent.
Example 2
Cd restoration based on graphite auxiliary primary battery2+A method of contaminating a medium, comprising the steps of:
(1) pretreatment of a polluted medium: passing through a 100-mesh sieve to Cd2+Adding a mixture of micron-level graphite powder and nano-level graphite powder with the mass fraction of 4% into a polluted medium (water body or soil), wherein graphite can float on the surface of the medium; for Cd2+0.8 percent (mass fraction) of potassium chloride is added into the polluted soil, and the two are mixed uniformly; the graphite powder purchased in the embodiment contains micron-scale and nano-scale graphite powder;
(2) the surface area is 20cm2Has a rectangular zinc plate and a surface area of 20cm2The surface of the rectangular copper plate is wrapped with cotton cloth and then Cd is vertically inserted from the upper part2+The depth of insertion in a polluted medium (water or soil) is 10cm, and the distance between electrodes (a zinc plate and a copper plate) is 20 cm;
(3) the zinc plate and the copper plate were connected by a copper wire, and the electrode reaction was maintained for 5 days.
The electrical parameter detection is carried out on the primary battery at the initial moment, which shows that the addition of the graphite can obviously improve the output current of the battery, and the output power of the battery is 25 mW. Simultaneously, ICP-OES (inductively coupled plasma emission spectrometer) is adopted to respectively measure the polluted soil or the pollution after 5 days of treatmentCd in water body2+The concentration of the obtained graphite can effectively promote Cd in the medium2+Removal of Cd from the polluted water2+The removal rate can reach 80 percent, and the removal rate of the polluted soil can reach 74 percent.
Example 3
Cd restoration based on graphite auxiliary primary battery2+A method of contaminating a medium, comprising the steps of:
(1) pretreatment of a polluted medium: passing through a 500-mesh sieve to Cd2+Adding a mixture of micron-level graphite powder and nano-level graphite powder with the mass fraction of 10% into a polluted medium (water body or soil), wherein graphite can float on the surface of the medium; for Cd2+1.6 percent (mass fraction) of potassium chloride is added into the polluted soil, and the two are mixed uniformly; the graphite powder purchased in the embodiment contains micron-scale and nano-scale graphite powder;
(2) the surface area is 100cm2Has a rectangular zinc plate and a surface area of 100cm2The surface of the rectangular copper plate is wrapped with cotton cloth and then Cd is vertically inserted from the upper part2+The depth of insertion in a polluted medium (water body or soil) is 30cm, and the distance between electrodes (a zinc plate and a copper plate) is 150 cm;
(3) the zinc plate and the copper plate were connected by a copper wire, and the electrode reaction was maintained for 10 days.
The electrical parameter detection is carried out on the primary battery at the initial moment, which shows that the addition of the graphite can obviously improve the output current of the battery, and the output power of the battery is 18 mW. Simultaneously, ICP-OES (inductively coupled plasma emission spectrometer) is adopted to respectively measure Cd in the polluted soil or the polluted water after 10 days of treatment2+The concentration of the obtained graphite can effectively promote Cd in the medium2+Removal of Cd from the polluted water2+The removal rate can reach 74 percent, and the removal rate of the polluted soil can reach 68 percent.
Example 4
This embodiment is different from embodiment 1 in that: the mass fraction of the graphite powder in the polluted medium is 15%.
Cd in this example2+The removal rate was similar to that of example 1.
Comparative example 1
This comparative example differs from example 2 in that: micro-nano-grade graphite powder is not added.
Example 5
Comparison of the output Current and Cd in comparative example 1 and example 22+The removal efficiency was measured, and the measurement results are shown in fig. 2 and 3.
As can be seen from FIG. 2, the output current of the primary cells with graphite added at 0h,4h,16h and 48h is higher than that of the cells without graphite, and as can be seen from FIG. 3, after the primary cells with 0.5g of graphite are treated for 5 days, Cd in the soil at 1cm,2cm and 3cm2+The removal efficiency is obviously improved, and Cd in the primary battery added with graphite2+The removal efficiency increases with increasing soil depth, i.e. Cd2+The content is inversely related to the depth of the medium. Therefore, the deep Cd of the medium can be added after the graphite is added2+Extracting.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. Cd restoration based on graphite auxiliary primary battery2+A method of contaminating a medium, characterized by: the method comprises the following steps:
(1) pretreatment of a polluted medium: adding micron and/or nanometer level graphite powder into the polluted medium;
(2) coating the surfaces of the zinc plate and the copper plate with an isolating medium and then inserting Cd2+In a contaminated medium;
(3) the zinc plate and the copper plate are connected through a copper wire, and the electrode reaction is maintained for more than 2 days.
2. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+Method for contaminating a medium, in particularCharacterized in that: the isolation medium is cotton cloth.
3. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 22+A method of contaminating a medium, characterized by: the mass fraction of the graphite powder in the polluted medium is 0.2-10%.
4. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: the contaminated medium is water.
5. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: the pollution medium is soil, and potassium chloride is added into the soil, wherein the addition amount of the potassium chloride is 0.01-1.6% of the mass of the soil.
6. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: the zinc plate is rectangular, and the surface area of the zinc plate is 2-100m2。
7. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: the copper plate is rectangular, and the surface area of the copper plate is 2-100m2。
8. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: the insertion depth of the zinc plate is 1-30cm, the insertion depth of the copper plate is 1-30cm, and the distance between the zinc plate and the copper plate is 2-150 cm.
9. Graphite-based assisted galvanic cell remediation Cd as claimed in claim 12+A method of contaminating a medium, characterized by: and (4) maintaining the electrode reaction for 2-10 days in the step (3).
CN202011138686.2A 2020-10-22 2020-10-22 Cd restoration based on graphite auxiliary primary battery2+Method for contaminating a medium Pending CN112371718A (en)

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