CN109896599A - A kind of metal reduction-electricity Fenton-like system and its application - Google Patents
A kind of metal reduction-electricity Fenton-like system and its application Download PDFInfo
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- CN109896599A CN109896599A CN201910248638.XA CN201910248638A CN109896599A CN 109896599 A CN109896599 A CN 109896599A CN 201910248638 A CN201910248638 A CN 201910248638A CN 109896599 A CN109896599 A CN 109896599A
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Abstract
The invention discloses a kind of metal reduction-electricity Fenton-like systems, it is restored using the metal ion in the self-discharge processes driving Fenton-like system of the capacitor after charging, and the circulation of metallic catalyst is effectively facilitated, avoid the problems such as existing electrochemical process is restricted by waste water electric conductivity；Metal reduction-electricity Fenton-like system of building is applied to processing simulated wastewater, shows higher effect efficiency and cyclical stability, and the wastewater treatment process being related to is simple, it is easy to operate, low energy consumption, environmental-friendly, it is with important application prospects.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of metal reduction-electricity Fenton-like system and its application.
Background technique
In recent years, with the high speed development and living standard and quality of life of the sharp increase of population, industry and agricultural
Continuous improvement, the mankind increasingly increase the demand of chemical substance；And in application process industrial wastewater and sanitary wastewater with
And residues of banned pesticides are discharged into water body by rainwash, and the type of Organic Pollutants In Water and concentration presentation is caused to rise year by year
Trend.Since organic chemical contaminant stable structure, the toxicity in waste water are big, traditional physico-chemical process, chemical method and bioanalysis and
Its correlation combiner method is difficult to reach satisfactory treatment effect.
Fenton oxidation method is by Fe (II) or Fe (III) and H2O2Reaction generates the hydroxyl radical free radical with strong oxidizing property,
Non-selectivity degradable organic pollutant a kind of high efficiency technical.Fenton oxidation method is simple with equipment, reaction condition is mild,
The advantages that reaction rate is fast and pollutant removal is thorough is especially showed when handling highly toxic persistence organic pollutant
Preferable effect out, therefore receive the extensive concern of researcher.
Although Fenton oxidation method has been one hundred years of history, some lack is remained in industrial application
Point: 1) such as Fe (II) and H2O2Between reaction rate it is very fast, usually react half a minute after, Fe (II) is substantially completely oxidized
For Fe (III)；2) Fe (III) and H generated2O2Reaction it is very slow, and Fe (III) is easily precipitated, and causes ferrikinetics difficult, H2O2's
Utilization rate is low.In order to solve the problems, such as that Fe (III) recycles hardly possible, reducing agents such as photo-reduction, electroreduction and ascorbic acid, azanol etc.
Mode is used for Fe (II)/Fe (III) circulation.Wherein electroreduction technology does not easily cause secondary dirt using electronics as cleaning agents
Dye, consersion unit be simply convenient for the advantages such as automatic management and by researcher's extensive concern；However, in poor useless of electric conductivity
In water, electrolyte need to be additionally added, secondary pollution problem easily is caused to water body.If not adding electrolyte, electrode pole can be caused
Change, so that a series of side reactions such as electrolysis water occur, which, which not only reduces current efficiency, can also reduce electrode life.Cause
This, significantly limits its practical application in practical water process.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of metal reduction-electricity Fenton body
System is constructed metal reduction-electricity Fenton-like system, is avoided electrochemical process by waste water electric conductivity using the capacitor after charging as cathode
Secondary pollution problem caused by the problems such as restriction and the existing additional electrolyte of wastewater electrochemical treatment treatment process, to organic contamination
Object shows excellent treatment effeciency.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of metal reduction-electricity Fenton-like system utilizes the self-discharge processes of the capacitor after charging using single electrode system
High volence metal ion in driving Fenton-like system is reduced into low valence metal ion, forms electric Fenton-like system.
In above scheme, the electricity Fenton-like system includes capacitor, catalyst and the oxidant after charging.
In above scheme, the charge volume of the capacitor is 0.01-1000mC.
Preferably, the charge volume of the graphite plate capacitor is 100-1000mC.
In above scheme, the cathode that the capacitor uses is carbons electrode；Stable charging performance and electrification can be taken into account
Oxidation susceptibility is learned, is conducive to construct metal reduction-electricity Fenton-like system, and show excellent catalytic degradation performance.
Preferably, the carbons electrode can be selected graphite paper, graphite plate, graphene, carbon nanotube, acetylene black, it is conductive it is black,
One or more of charcoal etc.；The metal oxide-type electrode can be selected ruthenium-oxide, yttrium oxide, manganese oxide, nickel oxide,
Titanium oxide, zinc oxide, copper oxide, aluminium oxide, vanadium oxide, chromium oxide, lead oxide, barium monoxide, calcium oxide, iron oxide, magnesia,
One or more of cobalt oxide etc.；Metal oxide/the carbon composite electrode by metal oxide and carbon material by (0.01~
100): 1 mass ratio mixes, and wherein metal oxide is ruthenium-oxide, yttrium oxide, manganese oxide, nickel oxide, titanium oxide, oxygen
Change zinc, copper oxide, aluminium oxide, vanadium oxide, chromium oxide, lead oxide, barium monoxide, calcium oxide, iron oxide, magnesia, cobalt oxide etc.
One or more of, carbon material is in graphite paper, graphite plate, graphene, carbon nanotube, acetylene black, conductive black, charcoal etc.
One or more.
A kind of above-mentioned metal reduction-electricity Fenton-like system processing organic wastewater field in application, specific steps include: by
Graphite plate capacitor after charging is placed in waste water reactor, and catalyst and oxidant is then added, and forms reaction solution, and in room
It is reacted under the conditions of gentle agitation, realizes the degradation of organic waste organic pollutants.
In above scheme, the catalyst is high valence transition metal ion or its corresponding oxide, oxidant are peroxide
Compound.
In above scheme, iron ion, copper ion, manganese ion, cobalt ions or nickel is can be selected in the high valence transition metal ion
Ion etc..
In above scheme, hydrogen peroxide, peroxy-monosulfate or peroxydisulfate etc. is can be selected in the peroxide.
In above scheme, the concentration of catalyst is 0.01-1.0mM in the reaction solution；The concentration of oxidant in reaction solution
For 0.01-2.0mM.
Preferably, the concentration range of the catalyst is 0.2-1.0mM, and the concentration range of oxide is 0.5-2.0mM.
Compared with prior art, the invention has the benefit that
1) present invention firstly provides electrochemistry single electrode system is used, metal reduction-electricity Fenton-like system is constructed, with individually electricity
Container electrode self-discharge processes driving metal ion reduction in the solution, and metallic catalyst efficient circulation is effectively facilitated, can have
Effect avoid existing electrochemical process by waste water electric conductivity limited and the existing additional electrolyte of wastewater electrochemical treatment treatment process caused by
Secondary pollution problem, the organic wastewater high for difficult to degrade, toxicity equally have good removal effect, and applicability is wide.
2) the metal reduction-electricity Fenton-like system for constructing the present invention is applied to processing repefral (DMP) mould
Quasi- waste water, can express higher effect efficiency and cyclical stability, and the wastewater treatment process being related to is simple, easy to operate,
It is environmental-friendly, a new thought can be provided for efficient Technologies for Organic Wastewater Treatment.
Detailed description of the invention
Fig. 1 be in embodiment building graphite plate capacitor under the different charging time corresponding chronopotentiometry spectrum and its
Capacitance comparison diagram.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, the building of the graphite plate capacitor of use and charging method include the following steps:
Using the titanium ruthenium plate of 10.0 × 4.0 × 0.1cm as anode, the graphite plate of 2.0 × 4.0 × 0.1cm is cathode, with 1.0M
Na2SO4Solution is electrolyte, and DC power supply constructs graphite plate capacitor charging apparatus, using constant current as power supply is provided
Mode obtains the graphite plate capacitor of different charge volumes, using chronopotentiometry under the different charging time
(Chronopotentiometry) (the result is shown in Figure 1) is measured to the capacitor after charging, the results showed that close with constant current
Degree is -6.25mA/cm2It charges, with 0.125mA/cm2Current density is discharged, in the charging time within the scope of 0-30s,
The discharge time of gained graphite plate capacitor is directly proportional to the charging time, wherein storage electricity is 152.3mC when charging 30s；
When charging time increases to 60s from 30s, storage electricity increases to 163.8mC.
Embodiment 1
Feasibility study
A kind of metal reduction-electricity Fenton-like system, it includes graphite plate capacitor (cathode), the catalyst (sulfuric acid after charging
Iron) and oxidant (H2O2), wherein the density of charging current of graphite plate capacitor is -6.25mA/cm2, charging time 30s fills
Electricity is 152.3mC.
By metal reduction-electricity Fenton-like system of the present embodiment building applied to the processing of DMP simulated wastewater, specific steps packet
It includes: hydrogen peroxide and ferric sulfate being added in DMP simulated wastewater, then the graphite capacitor after charging is put into waste water and is formed
Reaction solution, the wherein initial concentration [DMP] of DMP0For 0.1mM, H2O2Initial concentration [H2O2]0For 1.0mM, iron ion it is initial
Concentration [Fe3+]0For 0.5mM, DMP simulated wastewater volume is 60mL；Then it is reacted under the conditions of 20 ± 1 DEG C of temperature, carries out DMP
Catalytic degradation.
Metal reduction-electricity Fenton-like system that the present embodiment is formed is put with after uncharged graphite plate capacitor, charging respectively
The catalytic degradation system comparison that the graphite plate capacitor of electricity is formed, specific test result are shown in Table 1.
Influence of 1 capacitor charging/discharging of table to DMP treatment effect
| Reaction time/min | Removal rate/% of the uncharged system to DMP | Removal rate/% of the system of discharging after charging to DMP | Removal rate/% of the charging system to DMP |
| 0 | 0.00 | 0.00 | 0.00 |
| 1 | 5.23 | 6.72 | 12.99 |
| 2.5 | 7.96 | 8.96 | 29.65 |
| 5 | 11.48 | 15.48 | 44.77 |
| 10 | 21.05 | 25.05 | 67.26 |
| 15 | 33.22 | 36.22 | 84.90 |
| 20 | 45.45 | 47.45 | 95.01 |
The above results show: electric discharge gained graphite sheetmetal reduction-electricity Fenton-like system has DMP after uncharged and charging
Certain removal effect, but handle after 20min to the removal rate of DMP less than 50%；And use the graphite that charges obtained by the present embodiment
Metal reduction-electricity Fenton-like system removal effect that plate is formed is improved significantly, and removal rate is up to 95.01% after 20min, table
Metal reduction-electricity Fenton-like system that the bright present invention constructs has extraordinary treatment effect to DMP.
Embodiment 2
Influence research of the charging time to water treatment effect
By graphite plate capacitor application obtained by the different charging time in building metal reduction-electricity Fenton-like system, and handle DMP
Simulated wastewater, concrete operations condition include: [DMP]0=0.1mM, [H2O2]0=1.0mM, [Fe3+]0=0.5mM, pH0=3.0,
Wastewater volume is 60mL, and T=20 ± 1 DEG C, the density of charging current of graphite plate capacitor is -6.25mA/cm2, the charging time point
It Wei not 0s, 5s, 15s, 30s and 60s；Gained metal reduction-electricity Fenton-like system catalytic degradation effect is shown under different charge conditions
Table 2.
Influence of the different charging time of table 2 to DMP treatment effect
The above results show: when graphite plate capacitor charge time is improved from 0s to 30s, handling after 20min in waste water
The removal rate of DMP is increase gradually to 95.01% from 45.45%, and removal effect is obviously improved；Between when charging from 30s improve to
When 60s, DMP removal effect is only improved to 96.49%；Illustrate that charging time range can express excellent catalysis in 20-60s
Degradation efficiency.
Embodiment 3
Influence research of the concentration of hydrogen peroxide to water treatment effect
To gained metal reduction under the conditions of different concentration of hydrogen peroxide-electricity Fenton-like system processing DMP simulated wastewater effect
It is studied, concrete operations condition includes: [DMP]0=0.1mM, [Fe3+]0=0.5mM, wastewater volume 60mL, T=20 ± 1
DEG C, the density of charging current of graphite plate capacitor is -6.25mA/cm2, the charging time is 30s (charge volume 152.3mC),
[H2O2]0Respectively 0mM, 0.2mM, 0.5mM, 1.0mM and 2.0mM；Gained metal reduction-under the conditions of different concentration of hydrogen peroxide
The catalytic degradation effect of electric Fenton-like system is shown in Table 3.
Influence of 3 concentration of hydrogen peroxide of table to DMP treatment effect
The above results show concentration of hydrogen peroxide from 0 increase to 1.0mM when, handle 20min after DMP in waste water is gone
Except rate is increase gradually to 95.01% from 45.45%, removal effect is obviously improved；When concentration is improved to 2.0mM, DMP removal effect
Fruit is only improved to 97.10%；Illustrate that concentration of hydrogen peroxide range can express excellent catalytic degradation effect in 1.0-2.0mM
Rate.
Embodiment 4
Influence research of the ferric ion concentration to water treatment effect
To gained metal reduction under the conditions of different ferric ion concentrations-electricity Fenton-like system processing DMP simulated wastewater effect
Fruit is studied, and concrete operations condition includes: [DMP]0=0.1mM, [H2O2]0=1.0mM, wastewater volume 60mL, T=20
± 1 DEG C, the density of charging current of graphite plate capacitor is -6.25mA/cm2, the charging time is 30s (charge volume 152.3mC),
[Fe3+]0Respectively 0mM, 0.1mM, 0.2mM, 0.5mM and 1.0mM；Metal obtained by under the conditions of difference ferric ion concentrations excessively is also
The catalytic degradation effect of former-electric Fenton-like system is shown in Table 4.
Influence of 4 ferric ion concentration of table to DMP treatment effect
The above results show: ferric ion concentration from 0 increase to 0.5mM when, handle 20min after to DMP in waste water
Removal rate is increase gradually to 95.01% from 3.99%, and removal effect is obviously improved；When concentration is improved to 1.0mM, DMP removal
Effect is only improved to 98.41%；Illustrate that ferric ion concentration range can express excellent catalytic degradation in 0.5-1.0mM
Efficiency.
Embodiment 5
Stable circulation Journal of Sex Research
Metal reduction-electricity the Fenton-like system constructed to the present invention is recycled, and grinds to effect is recycled
Study carefully, concrete operations condition includes: [DMP]0=0.1mM, [H2O2]0=1.0mM, [Fe3+]0=0.5mM, graphite plate capacitor
The density of charging current is -6.25mA/cm2, the charging time is 30s (charge volume 152.3mC), wastewater volume 60mL, T=20
± 1 DEG C, difference is recycled gained DMP treatment effect test result under times condition and is shown in Table 5.
Influence of 5 cycle-index of table to DMP treatment effect
The above results charge again after showing graphite plate capacitor use of the present invention, still keep good to DMP
Degrading activity, illustrate gained graphite plate capacitor it is with good stability.
The present invention is not only limited to foregoing description, it is noted that for those of ordinary skill in the art, is not taking off
Under the premise of from the invention design, several modifications and variations can also be made, these are all within the scope of protection of the present invention.
Such as in graphite plate capacitor charging process, capacitor can be prepared with other carbon materials or metal oxide, (such as with other acid
Hydrochloric acid etc.), alkali (such as potassium hydroxide) or inorganic salts (such as sodium sulphate) be used as electrolyte, with other transition metal ions salts
(such as copper ion) is used as catalyst, uses other peroxide (such as persulfate) as oxidant；And these change or change
Into all belonging to the scope of protection of the present invention.
Claims (10)
1. a kind of metal reduction-electricity Fenton-like system, which is characterized in that use single electrode system, utilize the capacitor after charging
Self-discharge processes drive the metal ion reduction in Fenton-like system, form metal reduction-electricity Fenton-like system.
2. metal reduction-electricity Fenton-like system according to claim 1, which is characterized in that the charge volume of the capacitor is
0.01-1000mC。
3. metal reduction-electricity Fenton-like system according to claim 1, which is characterized in that the charge volume of the capacitor is
150-1000mC。
4. metal reduction-electricity Fenton-like system according to claim 1, which is characterized in that the yin used in the capacitor
Extremely carbons electrode, metal oxide-type electrode or metal oxide/carbon composite electrode.
5. metal reduction-electricity Fenton-like system according to claim 4, which is characterized in that the material that the carbons electrode is selected
Material is one or more of graphite paper, graphite plate, graphene, carbon nanotube, acetylene black, conductive black, charcoal.
6. metal reduction-electricity Fenton-like system according to claim 4, which is characterized in that the metal oxide-type electrode
The material of selection is ruthenium-oxide, yttrium oxide, manganese oxide, nickel oxide, titanium oxide, zinc oxide, copper oxide, aluminium oxide, vanadium oxide, oxygen
Change one or more of chromium, lead oxide, barium monoxide, calcium oxide, iron oxide, magnesia, cobalt oxide.
7. metal reduction-electricity Fenton-like system according to claim 4, which is characterized in that the metal oxide/carbon is compound
Electrode presses (0.01~100) by metal oxide and carbon material: 1 mass ratio is combined.
8. application of any one of the claim 1~7 metal reduction-electricity Fenton-like system in processing organic wastewater field,
It is characterized in that, specific steps include: that the capacitor after charging is placed in waste water reactor, and catalyst and oxidation is then added
Agent forms reaction solution, and is reacted at room temperature.
9. application according to claim 8, which is characterized in that the catalyst is high valence transition metal ion or its correspondence
Oxide；Oxidant is peroxide.
10. application according to claim 8, which is characterized in that the concentration of catalyst is 0.01- in the reaction solution
1.0mM；The concentration of oxidant is 0.01-2.0mM in reaction solution.
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| CN111252865A (en) * | 2020-02-19 | 2020-06-09 | 燕山大学 | Method for treating organic wastewater by electrochemical synergistic peroxyacetic acid system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111252865A (en) * | 2020-02-19 | 2020-06-09 | 燕山大学 | Method for treating organic wastewater by electrochemical synergistic peroxyacetic acid system |
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Application publication date: 20190618 |