CN110117045A - A kind of process for treating heavy-metal waste water based on bimetallic hot recycling amino battery - Google Patents
A kind of process for treating heavy-metal waste water based on bimetallic hot recycling amino battery Download PDFInfo
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- CN110117045A CN110117045A CN201910277030.XA CN201910277030A CN110117045A CN 110117045 A CN110117045 A CN 110117045A CN 201910277030 A CN201910277030 A CN 201910277030A CN 110117045 A CN110117045 A CN 110117045A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/4608—Treatment of water, waste water, or sewage by electrochemical methods using electrical discharges
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/182—Regeneration by thermal means
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
- C02F2201/46185—Recycling the cathodic or anodic feed
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Abstract
The invention discloses a kind of process for treating heavy-metal waste water based on bimetallic hot recycling amino battery.Make anode with metal Zn, may be constructed Ag/Zn, Cu/Zn, Co/Zn and Ni/Zn bimetallic hot recycling amino battery.The waste water of metal ion (Ag, Cu, Co or Ni) is passed through cathode chamber, ammonia is passed through in the anode compartment, discharges.Using metal ion during electric discharge in the sedimentary effect of cathode, achieve the purpose that wastewater treatment.After one processing cycle, treated waste water in cathode chamber is discharged, continues to be passed through heavy metal wastewater thereby to be processed being handled.After several circulations, ammonia density is reduced in anolyte, to reduce ion remaval efficiency.At this moment hot recycling is carried out to anolyte using waste thermal energy, the ammonia distilled out is passed through the processing cycle that new anolyte starts a new round.The present invention, which is realized, can convert high-power electric energy for low-grade exhaust heat while handling heavy metal ions in wastewater.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to an a kind of huge sum of money based on bimetallic hot recycling amino battery
Belong to wastewater treatment method.
Background technique
Water pollution is the important environmental problem of an influence whole world human survival, wherein opening from industrial production, mining industry
It adopts the waste water containing heavy metal ion discharged with industries such as battery manufactures and brings the ecology and survival pressure of most serious, mainly
Because of the permanent and toxicity of heavy metal pollution.Therefore, the discharge and processing of effluent containing heavy metal ions need more safe and efficient
And environmental protection, to ensure the health of human lives and the sustainable development of society.In recent years, UF membrane, coagulation and it is reverse osmosis etc. very
More technologies all realize higher removal efficiency, but the problems such as higher material or operating cost and high energy consumption limits big rule
The development of mould substance.Recently, some wastewater processing technologies can export certain electricity while realizing metal ion removal
Can, or energy is provided for processing unit using solar energy and triboelectricity, operating cost can be greatly reduced in this, have preferable
Application prospect, especially in the place of some remote poverties.But the output power of these technologies and energy density are also at present
Smaller, removal efficiency also has to be hoisted.
Summary of the invention
For prior art scenario, the invention proposes a kind of heavy metal wastewater therebies based on bimetallic hot recycling amino battery
Low-grade exhaust heat can be converted to electric energy while efficiently removing the heavy metal ion in waste water, and had by processing method
There are higher power and energy density.
In order to solve the above-mentioned technical problems, the present invention provides a kind of heavy metals based on bimetallic hot recycling amino battery
Wastewater treatment method includes the following steps:
1) waste water containing heavy metal ion is passed through cathode chamber, and ammonium hydroxide is added in the anode compartment, discharged, generate electricity
Energy；In discharge process, in cathode deposition reaction occurs for heavy metal ion, and with the progress of electric discharge, concentration of heavy metal ion can subtract
It is small, to reach the purpose of wastewater treatment；
2) when cell voltage is reduced to zero or cathode generates a large amount of bubbles evolving hydrogen reaction occurs, electric discharge cut-off completes the
The wastewater treatment of one circulation, and the catholyte wastewater collection containing reduction ion concentration is got up by treated；
It is passed through the new waste water containing heavy metal ion into cathode chamber to discharge, is changed without anolyte, starts second
Processing cycle；
3) repeat step 2) until cathode ion removal efficiency is greatly reduced, entered step 4) lower than 50%；
Since oxidation reaction occurs for anode, the metal ion and ammonia of generation form complex, the concentration of anode ammonia can be reduced, to reduce
Anode potential and cell voltage, while will cause the reduction of cathode ion removal efficiency；
4) anolyte is passed through destilling tower and can be carried out hot recycling using waste heat, the ammonia isolated is passed through to new sun again
Pole liquid carries out the wastewater treatment of a new round.
When anode be metal Zn, and in cathode chamber initial electrode liquid be ammonium sulfate ((NH4)2SO4) and respective metal sulfuric acid
Salt, initial electrolysis liquid is ammonium sulfate ((NH in anode chamber4)2SO4) and when ammonium hydroxide, be passed through in cathode chamber containing Cu (II), Co (II) and
One of Ni (II) three kinds of ions or a variety of waste water are handled.
When anode be metal Zn, and in cathode chamber initial electrode liquid be ammonium nitrate (NH4NO3) and respective metal nitrate,
Initial electrolysis liquid is ammonium nitrate (NH in anode chamber4NO3) and when ammonium hydroxide, be passed through in cathode chamber containing Cu (II), Co (II), Ni (II)
It is handled with one of Ag (I) four kinds of ions or a variety of waste water.
When anode be Ni metal, and in cathode chamber initial electrode liquid be ammonium nitrate (NH4NO3) and respective metal nitrate,
Initial electrolysis liquid is ammonium nitrate (NH in anode chamber4NO3) and when ammonium hydroxide, be passed through the waste water containing Ag (I) in cathode chamber and handled.
Ammonia concn is 1-4M in the anode chamber.
The indoor stirrer of cathode is stirred waste water.
Electrolyte in the cathode chamber or anode chamber is flow regime.
Oxygen-free inert gas, removal oxygen and inhibition electrode corrosion are passed through in the cathode chamber or anode chamber.
Process for treating heavy-metal waste water provided by the invention based on bimetallic hot recycling amino battery, it is useless compared to other
Water treatment technology, beneficial effect are:
1. making anode using metal Zn, it is a variety of heavy that Cu in waste water (II), Co (II), Ni (II) and Ag (I) etc. can be removed
Metal ion.
2. utilizing based on low-grade exhaust heat, electric energy, and double gold can produce while removing heavy metal ions in wastewater
Belonging to electrode design helps to promote discharge voltage and power density and energy density.
3. being to remove the Cu in waste water (II) based on Cu/Zn bimetallic hot recycling amino battery (Cu/Zn-TREB)
Example, for Cu (II) waste water of the concentration range containing 0.002-0.3M wider, 90% or more removal is may be implemented in Cu/Zn-TREB
Efficiency, while the power density exported increases with concentration and is increased, and is 31-546W m-2- electrode, energy density is with concentration
It is linearly increasing, it is 42-4888W h m-3-total volume.For Cu (II) waste water containing 0.05M, Cu/Zn-TREB is not
8 efficient processing cycles can be carried out under conditions of replacement anolyte (removal efficiency is greater than 90%).
4. being to remove the Co in waste water (II) based on Co/Zn bimetallic hot recycling amino battery (Co/Zn-TREB)
Example, for Co containing 0.01-0.1M (II) waste water, Co (II) removal efficiency that Co/Zn-TREB may be implemented is 85-90%, defeated
Power density out increases with concentration and is increased, and is 23-123W m-2-electrode。
5. being to remove the Ni in waste water (II) based on Ni/Zn bimetallic hot recycling amino battery (Ni/Zn-TREB)
Example, for Ni containing 0.01M (II) waste water, it is 87% that Ni (II) removal efficiency, which may be implemented, in Ni/Zn-TREB, and the power of output is close
Degree is 20W m-2-electrode。
Detailed description of the invention
Fig. 1 is the mistake for removing Cu in waste water (II) based on Cu/Zn bimetallic hot recycling amino battery (Cu/Zn-TREB)
Journey schematic diagram.
Fig. 2 (A) is 1M (NH4)2SO4、2M NH3Under the conditions of, the removal of Cu/Zn-TREB under different initial Cu (II) concentration
Efficiency, cathode and anode coulombic efficiency；
Fig. 2 (B) is 1M (NH4)2SO4、2M NH3, under the conditions of initial Cu (II) concentration is 0.002M, handle the time to Cu/
The influence of Zn-TREB removal efficiency, cathode and anode coulombic efficiency.
Fig. 3 (A) is 1M (NH4)2SO4、2M NH3Under the conditions of, the output of Cu/Zn-TREB under different initial Cu (II) concentration
Power density with current density variation；
Fig. 3 (B) is 1M (NH4)2SO4、2M NH3Under the conditions of, the electrode of Cu/Zn-TREB under different initial Cu (II) concentration
Potential with current density variation.
Fig. 4 (A) is 1M (NH4)2SO4、2M NH3Under the conditions of, Cu/Zn-TREB is entire under different initial Cu (II) concentration
Output power density changes with time in wastewater treatment circulation；
Fig. 4 (B) is 1M (NH4)2SO4、2M NH3Under the conditions of, Cu/Zn-TREB is entire under different initial Cu (II) concentration
Electrode potential changes with time in wastewater treatment circulation.
Fig. 5 is 1M (NH4)2SO4、2M NH3Under the conditions of, Cu/Zn-TREB entire wastewater treatment circulation in output power and
The relationship of energy density and initial Cu (II) concentration.
Fig. 6 (A) is 1M (NH4)2SO4、2M NH3, under the conditions of initial Cu (II) concentration is 0.05M, Cu/Zn-TREB is more
Output power density changes with time in a continuous wastewater treatment circulation；
Fig. 6 (B) is 1M (NH4)2SO4、2M NH3, under the conditions of initial Cu (II) concentration is 0.05M, Cu/Zn-TREB is more
Electrode potential changes with time in a continuous wastewater treatment circulation.
Fig. 7 (A) is 1M (NH4)2SO4、2M NH3, under the conditions of initial Cu (II) concentration is 0.05M, Cu/Zn-TREB is more
The variation of peak power density and removal efficiency in a continuous wastewater treatment circulation；
Fig. 7 (B) is 1M (NH4)2SO4、2M NH3, under the conditions of initial Cu (II) concentration is 0.05M, Cu/Zn-TREB is more
The variation of removal efficiency, cathode and anode coulombic efficiency and energy density in a continuous wastewater treatment circulation.
Fig. 8 (A) is 1M (NH4)2SO4、2M NH3Under the conditions of, initial Cu (II), Co (II) and Ni (II) concentration are 0.01M
When, output power density is at any time in each comfortable entire wastewater treatment circulation of Cu/Zn-TREB, Co/Zn-TREB and Ni/Zn-TREB
Between variation, embedded figure gives the respective removal efficiency of Cu/Zn-TREB, Co/Zn-TREB and Ni/Zn-TREB, cathode and sun
Pole coulombic efficiency；
Fig. 8 (B) is 1M (NH4)2SO4、2M NH3Under the conditions of, initial Cu (II), Co (II) and Ni (II) concentration are 0.01M
When, electrode potential is at any time in each comfortable entire wastewater treatment circulation of Cu/Zn-TREB, Co/Zn-TREB and Ni/Zn-TREB
Variation.
Fig. 9 (A) is 1M (NH4)2SO4、2M NH3Under the conditions of, when initial Cu (II) and Co (II) concentration are 0.1M, Cu/
Output power density changes with time in each comfortable entire wastewater treatment circulation of Zn-TREB and Co/Zn-TREB, and embedded figure is given
The respective removal efficiency of Cu/Zn-TREB and Co/Zn-TREB, cathode and anode coulombic efficiency are gone out；
Fig. 9 (B) is 1M (NH4)2SO4、2M NH3Under the conditions of, when initial Cu (II) and Co (II) concentration are 0.1M, Cu/
Electrode potential changes with time in each comfortable entire wastewater treatment circulation of Zn-TREB and Co/Zn-TREB.
Specific embodiment
The present invention will be described in detail in the following with reference to the drawings and specific embodiments, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
In the description of the present invention, it is to be understood that, term "one", " multiple " " first ", the only table such as " second "
Registration amount or positional relationship are based on being merely for convenience of description of the present invention and simplification of the description shown in attached drawing, rather than instruction or dark
Specific quantity and position must be had, be operated with specific quantity and position by showing signified device or original part, therefore cannot be managed
Solution is limitation of the present invention.
Embodiment 1: Cu in waste water (II) is removed based on Cu/Zn bimetallic hot recycling amino battery (Cu/Zn-TREB)
Based on the concept of bimetallic hot recycling amino battery (B-TRAB), the present invention provides one kind to remove in waste water
The method of the heavy metal ion such as Cu (II), Co (II), Ni (II) and Ag (I), is mainly utilized the cathode of B-TRAB discharge process
Sedimentary effect and hot recycling process, referred to as bimetallic hot recycling electro-deposition battery (B-TREB).As shown in Fig. 1 (A), utilize
Cu/Zn bimetallic hot recycling electro-deposition battery (Cu/Zn-TREB) removes the process of Cu in waste water (II): will contain Cu's (II)
Waste water is passed through cathode chamber, and 2M ammonium hydroxide, the laggard horizontal high voltage electric discharge of connection Cu and Zn electrode are added in the anode compartment.In discharge process,
Cu (II) is deposited on Cu electrode in cathode chamber, and Zn electrode is oxidized to Zn (NH3) under ammonia effect in anode chamber4 2+。
Cu (II) concentration in waste water after one discharge cycles in cathode chamber substantially reduces, and achievees the purpose that wastewater treatment.Circulation knot
Shu Hou is changed without anolyte, continues Cu (II) waste water of high concentration to be passed through cathode chamber handling.It is carried out continuously several processing
After circulation, Zn (II) concentration increases in anolyte, reduces ammonia density, and anode performance is made to be deteriorated, to influence cathode ion
Removal efficiency.At this moment, the anolyte after using is passed through destilling tower and carries out hot recycling (such as Fig. 1 (B) using low-grade exhaust heat
It is shown), the ammonia distilled out is passed through anode chamber and forms new anolyte, starts the wastewater treatment of a new round.Hot recycling process institute
The thermal energy needed can be derived from industrial production and daily life a large amount of low-temperature waste heat energy, these waste thermal energies are directly discharged to ring
Serious greenhouse effects and environmental pollution are will cause in border.In addition, there is Zn (II) waste water of some high concentrations to produce after hot recycling
It is raw, but measure seldom, far below the amount of the waste water of multi-cycle processing.These can pass through the physics such as some absorption containing Zn (II) waste water
Means are handled, and can also be passed through microbiological fuel cell or be carried out next step energy as the electrolyte of Cu/Zn-TRAB
Amount recycling can use the electric energy of discharge process generation also to be handled by the efficient means such as coagulation.Multiple processing follow
After ring, Cu cathode quality increases, and Zn anode is corroded, but can be used for the charging process of Cu/Zn-TRAB, passes through anode and cathode
The recycling of electrode is realized in the conversion of function.
Battery tester: as shown in Fig. 1 (C), single Cu/Zn bimetallic hot recycling electro-deposition battery (Cu/Zn-
TREB) by anode chamber, cathode chamber (cylinder of long 4cm, diameter 3cm, by side length be 4cm organic glass cube processing and
At) and anionic membrane (AEM, Selemion AMV, Japan；Effective surface area is 7cm2) composition.Cathode is copper mesh (50
× 50mesh, McMaster-Carr；0.8cm × 2cm), anode is zinc metal sheet (with a thickness of 0.2mm, McMaster-Carr；
0.8cm×2cm).Two Ag/AgCl reference electrodes (+208mV relative to standard hydrogen electrode at 20 DEG C, Tianjin aida) point
It is not inserted on the external circuit beside two electrodes, for detecting the electrode potential of cathode and anode.Cathode chamber has a magnetic stir bar
(6.4 × 15.9mm, egg type, VWR, 500rpm) is sufficiently mixed electrolyte.
Electrolyte: the CuSO of various concentration is configured4(0.0005M, 0.002M, 0.01M, 0.05M, 0.1M, 0.3M, Alfa
Aesar)、CoSO4(0.01M and 0.1M, Alfa Aesar) and NiSO4(0.01M and 0.1M, Alfa Aesar) is used as catholyte
Carry out simulated wastewater, while in order to increase the conductivity of solution, (the NH of 1M is separately added into catholyte and anolyte4)2SO4
(Alfa Aesar) is used as electrolyte.The ammonium hydroxide (aladdin, AR, 25-28%) that initial anolyte also needs to be added 2M comes
Increase anode potential, promotes cell voltage.Different electrolyte is added electrode chamber and respectively constitutes Cu/Zn-TREB, Co/Zn-
TREB and Ni/Zn-TREB, (18~23 DEG C) progress all at room temperature of all Cell Experimentation Ans.
Test and calculation method: the polarization test of B-TREBs by a cell tester (Arbin Instruments,
BT-G it) completes.Electric current (I, A) scanning may be implemented by controlling external resistance, to obtain electrode potential and cell voltage
The variation of (U, V).Take slower scanning speed (1mA s-1), guarantee electrode as far as possible is in stable state.The battery current of acquisition and
The product of voltage is power (P, W).With the projected area (A=1.6cm of electrode2) based on, it is close that corresponding electric current can be obtained
Spend (Ia, Am-2) and power density (Pa, W m-2)。
In the experiment of removal heavy metal ions in wastewater, corresponding B-TREB is close to obtain peak power in polarization test
External resistance when spending carries out constant-resistance discharge, realizes and is carried out while Maximum Power Output using the ion deposition effect that cathode occurs
Wastewater treatment.For containing the waste water of Cu (II), Cu/Zn-TREB is carried out under different initial Cu (II) concentration with different extrernal resistances
Constant-resistance discharge (0.0005M, 200 Ω；0.002M,140Ω；0.01M,80Ω；0.05M,13Ω；0.1M,8Ω；0.3M,6.5
Ω).(a large amount of bubbles are precipitated on electrode, when evolving hydrogen reaction occurs) when cell voltage is reduced to 0.13-0.32V, electric discharge cut-off.
Because anode potential is larger, when cathode Cu (II) concentration reduces, the polarization of Cu (II) deposition increases, while it is anti-that liberation of hydrogen occurs
It answers, so cell voltage will not be reduced to 0V.Due to Cu (II) initial concentration difference, the bigger discharge resistance of concentration is smaller, electric current
Bigger, so that polarization increases, the potential that evolving hydrogen reaction occurs is also different, therefore blanking voltage increases with concentration and reduced
(0.0005 M,0.32V；0.002M,0.31V；0.01M,0.27V；0.05M,0.22V；0.1M,0.17V；0.3M,0.13V).
For containing the waste water of 0.01M and 0.1M Co (II), Co/Zn-TREB carries out constant-resistance respectively with the external resistance of 20 Ω and 10 Ω and puts
Electricity, blanking voltage are respectively~0.22V and~0.19V.For containing the waste water of 0.01MNi (II), Ni/Zn-TREB is with 20 Ω's
External resistance carries out constant-resistance discharge, and blanking voltage is respectively~0.14V.During ion remaval, the electric current of B-TREB, voltage with
And the electrode potential of cathode and anode is all recorded with the time interval of 1s.The quantity of electric charge (Q, C) shifted during this by Q=
∫ I dt is calculated.Energy density (E, W h m-3) obtained by E=∫ UI dt/V calculating, V is the total volume (56 mL) of electrolyte.Yin
The coulombic efficiency (CCE and ACE) of ion remaval efficiency (RE), cathode and anode in pole room is obtained by following formula:
Wherein, m0And mfThe respectively quality of the forward and backward cathode of wastewater treatment；Subscript c and a respectively indicate cathode and anode；ci
Indicate the initial concentration (i=Cu (II), Co (II) or Ni (II)) of i ion；VcFor the volume (28 ± 1mL) of catholyte；M is gold
Molal weight (the Cu:63.55g mol of category-1, Co:58.93g mol-1, Ni:58.69g mol-1, Zn:65.38g mol-1)； F
(96485C mol-1) it is Faraday constant；N (for Cu, Co, Ni and Zn, n=2) is the electron number of electrode process transfer.
In cycle performance test, each circulation Cu/Zn-TREB carries out constant-resistance discharge with 13 Ω external resistances and contains to handle
The waste water of 0.05M Cu (II).The catholyte more renewed after each circulation is handled, but is changed without anolyte, until removal is imitated
Stop loop test when rate is greatly reduced.The processing time of each circulation is 150min.Battery in each test loop
Electric current, voltage and electrode potential are all recorded, to obtain the coulombic efficiency and Cu of power and energy density, cathode and anode
(II) removal efficiency.When removal efficiency is greatly reduced, anolyte is passed through destilling tower and carries out hot recycling, the ammonia distilled out
It can be added in new anolyte, carry out the wastewater treatment of next round.The heat source that low-grade exhaust heat can be used as destilling tower has come
At this process.
Experimental result:
Removal efficiency of the Cu/Zn-TREB under different initial Cu (II) concentration: it can be seen that Cu (II) from Fig. 2 (A)
Removal efficiency can reach 90% or more when concentration is greater than 0.01M.When Cu (II) concentration is 0.002M, removal efficiency is
84.3%；When Cu (II) concentration drops to 0.0005M, removal efficiency only has 33.7%.Show the removal efficiency of Cu (II) by Cu
(II) in the case of the influence of concentration, especially low concentration.When Cu (II) concentration is 0.002M, the proper extension processing time can make
Removal efficiency increases to 92.7% from 84.3%, reduces processing time removal efficiency and is then reduced to 70.3%, therefore removal efficiency
Also it is subject to processing the influence of time (shown in such as Fig. 2 (B)).Therefore, when Cu (II) concentration is 0.002M-0.3M, Cu/Zn-TREB
Method can make the removal efficiency of Cu (II) reach 90% or more.
As shown in Fig. 2 (A), cathode coulombic efficiency (CCE) increases with Cu (II) concentration and is increased, and Cu (II) concentration is 0.1M
When with 0.3M, cathode coulombic efficiency (CCE) is close to 100%, because the side reaction of generation is less when Cu (II) concentration is larger.
When Cu (II) concentration is lower, hydroxide easy to form precipitates or forms complex with free ammonia, affects Cu's (II)
Electrodeposition process.In addition, the extension processing time also results in the reduction of cathode coulombic efficiency (CCE), because electric discharge latter stage is extremely low
When Cu (II) concentration, it may occur that evolving hydrogen reaction.Anode coulombic efficiency (ACE) is unrelated with Cu (II) concentration, in 60%~80%
Fluctuation.Zinc makees the coulombic efficiency of anode much higher than copper anode (30%-35%), this will be helpful to promote cycle performance.
Output power and energy density of the Cu/Zn-TREB in wastewater treatment process: contain the waste water phase of Cu (II) in processing
Between, peak power density increases with Cu (II) concentration and increases (0.0005M, 20W m-2；0.002M, 31W m-2；0.01M,
90W m-2；0.05M, 413W m-2；0.1M, 516W m-2；0.3M, 546W m-2, as shown in Fig. 3 (A)), this is mainly due to Cu
(II) concentration increase dramatically increases cathode potential (shown in such as Fig. 3 (B)).When Cu (II) concentration increases to 0.1M or more, peak
It is worth the increase amplitude reduction of power density, tends to definite value (as shown in Figure 5).
The Cu in waste water (II), various concentration are removed to obtain external resistance progress constant-resistance discharge when peak power density
Under complete cycle such as Fig. 4 (A) and (B) shown in.As shown in Fig. 4 (A), Cu (II) concentration is in 0.05M-0.3M, power density
Variation divide three phases, first increase to peak value and reduce rapidly again, the later period is substantially gentle；Cu (II) concentration is in 0.0005M-
When 0.01M, the variation of power density only has latter two stage.The variation of power density and the variation tendency of cathode potential are consistent
(shown in such as Fig. 4 (B)).It discharges latter stage, cathode potential is reduced to -0.8V or so, bubble spilling has been observed in experiment, shows to send out
Evolving hydrogen reaction is given birth to.Anode potential increases with cathode Cu (II) concentration and is reduced, because electric current increases when Cu (II) concentration is larger
Add, anode ammonia consumption increases, and causes anode potential to reduce, but influence degree is lower than cathode.In processing containing the useless of Cu (II)
During water, the energy density of Cu/Zn-TREB output linearly increases (as shown in Figure 5) with the increase of initial Cu (II) concentration.Cu
(II) energy density obtained when concentration is 0.1M is 1383W h m-3, when Cu (II) concentration increases to 0.3M, energy density increases
It is added to 4888W h m-3。
The cycle performance of Cu/Zn-TREB processing waste water: Cu/Zn-TREB when carrying out containing Cu (II) wastewater treatment, in order to
The usage amount for reducing anolyte is not that the replacement of anolyte is carried out after each circulation, but each circulation Zn anode
It will dissolve, Zn (II) meeting of dissolution and the ammonia in anolyte form complex, cause ammonia density in anolyte to reduce, to drop
Low cathode potential, and then influence the performance of Cu/Zn-TREB and the removal efficiency of Cu (II).Therefore, in order to examine cycle performance,
Using the Cu (II) of 0.05M as catholyte, 2M NH3Make anolyte, the experiment of Lai Jinhang Cu (II) waste water circular treatment.It is each to follow
Ring all uses new catholyte, anolyte without replacement, power density and electrode potential such as Fig. 6 (A) of each circulation and
(B) shown in.Preceding 8 circulations, the removal efficiency of Cu (II) is in 90% or more (shown in such as Fig. 7 (A)).6th, 7,8 three circulation
Removal efficiency can achieve 96%, mainly due to these three circulation cathode coulombic efficiencies increase to 98% from~90%, table
Bright less side reaction occurs in cathode.9th circulation removal efficiency is down to 13%, consumes mainly due to ammonia density in anolyte
To the greatest extent.From Fig. 6 (B), it can be seen that, with the increase of recurring number, anode potential is gradually reduced, and reduced amplitude is increasing；The
9 circulating anode potentials are too small and zinc electrode is insufficient to allow to corrode, but there have part zinc ammonia complex that reduction has occurred to be anti-
It answers, therefore also results in anode coulombic efficiency greater than 100% (shown in such as Fig. 7 (B)).
Peak power density is gradually decreased with the increase of circulation, and first circulation peak power density reaches 427W m-2, the
2-8 circulation peak power density maintains 200-300W m-2(such as Fig. 6 (A) and 7 (A) are shown).Energy density approximate trend
It is to increase with circulation and reduce, individual cycle fluctuates, and preceding 8 circulating energy density maintains 630-780W h m-3(such as
Shown in Fig. 7 (B)).This means that can maintain 8 efficient wastewater treatment circulations in the case where being changed without anolyte, be used only
Accumulated energy density about 5664W h m can be obtained in the case where 28mL anolyte-3, useless containing Zn (II) much higher than processing 28mL
Energy required for water (using coagulation technology about~1000W h m-3).For Cu (II) waste water of low concentration, the function of acquisition
Rate and energy density can reduce, but still can guarantee higher removal efficiency, and cycle performance can get a promotion；Vice versa for more highly concentrated
Cu (II) waste water of degree, the power and energy density of acquisition will increase, but cycle performance can be weakened.
Embodiment 2: it is based on Co/Zn or Ni/Zn bimetallic hot recycling amino battery (Co/Zn-TREB or Ni/Zn-TREB)
To remove Co in waste water (II) or Ni (II)
Using metallic zinc as anode, under the system that sulfate does electrolyte, Cu/Zn, Co/Zn and Ni/Zn may be constructed
Three kinds of bimetallic hot recycling amino batteries remove the Cu in waste water (II), Co (II) and Ni (II)；Electrolyte is done in nitrate
System under, Ag/Zn-TREB can also be constituted to remove the Ag in waste water (I).Anode is done with other metals, also may be constructed
Other bimetallic amino batteries, such as: Ag/Cu-TREB does anode with Cu to remove the Ag in waste water (I).But in view of Zn has
Have the non-pollution of higher anode coulombic efficiency and sulfate, mainly have studied at present Cu/Zn-TREB, Co/Zn-TREB and
Tri- kinds of bimetallic amino batteries of Ni/Zn-TREB, compared the removal efficiency and power output under various concentration.
Experimental result: the waste water for catholyte containing 0.01MCu (II), Co (II) and Ni (II) is obtaining maximum power
Constant-resistance discharge (Cu (II), 80 Ω are carried out under conditions of output；Co (II), 20 Ω；Ni (II), 20 Ω), as shown in Fig. 8 (A),
The peak power (~100W m of Cu/Zn-TREB-2) it is much higher than Co/Zn-TREB (~23W m-2) and Ni/Zn-TREB (~20W
m-2), the cathode potential mainly due to Cu (II) deposition is higher than the cathode potential of Co (II) and Ni (II) deposition (such as Fig. 8 (B) institute
Show).The removal efficiency of Co (II) and Ni (II) are respectively 85% and 87%, the removal efficiency 92% of slightly less than Cu (II), mainly
Since the cathode coulombic efficiency (51% and 69%) of Co and Ni is lower than 82% (as shown in the insertion figure in Fig. 8 (A)) of Cu.Show
Under low concentration, evolving hydrogen reaction is easier to occur on metal Co, and Ni takes second place, to cause lower coulombic efficiency.For
Waste water (0.1M Ni (II) and the 1M (NH of the Cu of higher concentration containing 0.1M (II) and Co (II)4)2SO4Mixing can generate sulfate precipitate
Nickel ammonium, solubility is lower, therefore does not account for the Ni (II) of high concentration temporarily), the peak power of Co/Zn-TREB promoted to~
123W m-2, but still obtained much smaller than Cu/Zn-TREB~516W m-2(shown in such as Fig. 9 (A)), mainly by cathode potential
It influences (shown in such as Fig. 9 (B)).Under higher concentration, the removal efficiency of Co (II) and Cu (II) all reach 90%, and keep higher
Coulombic efficiency (99% and 96%) (as shown in the insertion figure in Fig. 9 (A)), therefore can be by extending the processing time come into one
Step promotes removal efficiency.But the case where anode coulombic efficiency of Zn is again smaller than low concentration under high concentration, this will lead to cycle performance
It is deteriorated.
Although above in conjunction with attached drawing, invention has been described, and the invention is not limited to above-mentioned specific implementations
Mode, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to of the invention
Within protection.
Claims (8)
1. a kind of process for treating heavy-metal waste water based on bimetallic hot recycling amino battery, comprising the following steps:
1) waste water containing heavy metal ion is passed through cathode chamber, and ammonium hydroxide is added in the anode compartment, discharged, produced electricl energy；
2) when cell voltage is reduced to zero or cathode generates a large amount of bubbles generation evolving hydrogen reactions, electric discharge cut-off completes first
The wastewater treatment of circulation, and the catholyte wastewater collection containing reduction ion concentration is got up by treated；
It is passed through the new waste water containing heavy metal ion into cathode chamber to discharge, is changed without anolyte, starts second processing
Circulation；
3) repeat step 2) until cathode ion removal efficiency is lower than 50%, enter step 4)；
4) anolyte is passed through destilling tower and can be carried out hot recycling using waste heat, the ammonia isolated is passed through to new anode again
Liquid carries out the wastewater treatment of a new round.
2. the process for treating heavy-metal waste water according to claim 1 based on bimetallic hot recycling amino battery, feature
Be, when anode be metal Zn, and in cathode chamber initial electrode liquid be ammonium sulfate ((NH4)2SO4) and respective metal sulfate,
Initial electrolysis liquid is ammonium sulfate ((NH in anode chamber4)2SO4) and when ammonium hydroxide, be passed through in cathode chamber containing Cu (II), Co (II) and Ni
(II) one of three kinds of ions or a variety of waste water are handled.
3. the process for treating heavy-metal waste water according to claim 1 based on bimetallic hot recycling amino battery, feature
Be, when anode be metal Zn, and in cathode chamber initial electrode liquid be ammonium nitrate (NH4NO3) and respective metal nitrate, sun
Initial electrolysis liquid is ammonium nitrate (NH in pole room4NO3) and when ammonium hydroxide, be passed through in cathode chamber containing Cu (II), Co (II), Ni (II) and
One of Ag (I) four kinds of ions or a variety of waste water are handled.
4. the process for treating heavy-metal waste water according to claim 1 based on bimetallic hot recycling amino battery, feature
Be, when anode be Ni metal, and in cathode chamber initial electrode liquid be ammonium nitrate (NH4NO3) and respective metal nitrate, sun
Initial electrolysis liquid is ammonium nitrate (NH in pole room4NO3) and when ammonium hydroxide, be passed through the waste water containing Ag (I) in cathode chamber and handled.
5. the heavy metal containing wastewater treatment according to any one of claim 1 to 4 based on bimetallic hot recycling amino battery
Method, which is characterized in that the ammonia concn that the anode chamber is added is 1-4 M.
6. the heavy metal containing wastewater treatment according to any one of claim 1 to 4 based on bimetallic hot recycling amino battery
Method, which is characterized in that the indoor stirrer of cathode is stirred waste water.
7. the heavy metal containing wastewater treatment according to any one of claim 1 to 4 based on bimetallic hot recycling amino battery
Method, which is characterized in that the electrolyte in the cathode chamber or anode chamber is flow regime.
8. the heavy metal containing wastewater treatment according to any one of claim 1 to 4 based on bimetallic hot recycling amino battery
Method, which is characterized in that oxygen-free inert gas is passed through in the cathode chamber or anode chamber, removal oxygen and inhibition electrode are rotten
Erosion.
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| CN107892363A (en) * | 2017-12-18 | 2018-04-10 | 清华大学 | The water treatment facilities and method of a kind of synchronous electrogenesis and conversion high volence metal ion |
| CN108321399A (en) * | 2018-03-27 | 2018-07-24 | 天津大学 | Bimetallic hot recycling amino battery system, flow battery system and application method |
| CN208093653U (en) * | 2018-03-27 | 2018-11-13 | 天津大学 | Bimetallic hot recycling amino flow battery system experimental model |
| CN108977652A (en) * | 2018-09-12 | 2018-12-11 | 郑忆依 | A kind of resource utilization method of the waste water slag of cobalt metallurgy of nickel |
| CN208352435U (en) * | 2018-03-27 | 2019-01-08 | 天津大学 | Bimetallic hot recycling amino Cell Experimentation An model |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892363A (en) * | 2017-12-18 | 2018-04-10 | 清华大学 | The water treatment facilities and method of a kind of synchronous electrogenesis and conversion high volence metal ion |
| CN108321399A (en) * | 2018-03-27 | 2018-07-24 | 天津大学 | Bimetallic hot recycling amino battery system, flow battery system and application method |
| CN208093653U (en) * | 2018-03-27 | 2018-11-13 | 天津大学 | Bimetallic hot recycling amino flow battery system experimental model |
| CN208352435U (en) * | 2018-03-27 | 2019-01-08 | 天津大学 | Bimetallic hot recycling amino Cell Experimentation An model |
| CN108977652A (en) * | 2018-09-12 | 2018-12-11 | 郑忆依 | A kind of resource utilization method of the waste water slag of cobalt metallurgy of nickel |
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Application publication date: 20190813 |