CN105417638A - Heterogeneous electric Fenton system and preparation and application thereof - Google Patents
Heterogeneous electric Fenton system and preparation and application thereof Download PDFInfo
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- CN105417638A CN105417638A CN201510780799.5A CN201510780799A CN105417638A CN 105417638 A CN105417638 A CN 105417638A CN 201510780799 A CN201510780799 A CN 201510780799A CN 105417638 A CN105417638 A CN 105417638A
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- fenton system
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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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a heterogeneous electric Fenton system and preparation and application thereof. Specifically, the heterogeneous electric Fenton system is composed of a composite cathode electrode and an inert anode electrode in an electrolytic tank containing an electrolyte solution, the composite cathode electrode is prepared from graphene, metallic oxide, polytetrafluoroethylene and the like, and waste liquor which is about to be treated and contains contaminants is placed in the electric Fenton system for effective degradation.
Description
Technical field
The invention belongs to environment protection and sewage treatment area, be specifically related to heterogeneous Fenton system and Synthesis and applications thereof.
Background technology
Electro-Fenton process is one of high-level oxidation technology recently received much concern, and the OH utilizing electrochemical process electrolysis generation to have strong oxidizing property carrys out the organism in oxidized waste water.Fenton system, mainly in energising situation, produces H in cathodic area electrocatalysis
2o
2, in the solution with variable valency metal ions (as Fe
3+/ Fe
2+deng) reaction generation strong oxidizer hydroxyl radical free radical (OH), OH activity is high, and oxidation capacity is strong, even mineralising toxic organic pollutants of can effectively degrading.Relative to classical Fenton system, the H in solution
2o
2can continue in cathodic area to produce, meanwhile, the Fe that Fenton reaction produces
3+fe can be reduced in cathodic area
2+, Fenton is reacted and is continued, substantially increase the oxidation efficiency of Fenton reaction.The advantages such as therefore, it is simple that Fenton technology has equipment, processing ease, and operational efficiency is lasting.
But at present in the process using this system process waste water, need to regulate the pH of waste water to acid, constrain its industrial applications.Therefore, the pH scope how improving Fenton system process waste water is a research emphasis of Fenton technology.
In sum, current this area still lacks the effective means of the pH value range improving Fenton system process waste water.Therefore, this area can at the Fenton system of wider pH scope, efficient work in the urgent need to developing, to be applied to the occasions such as sewage disposal.
Summary of the invention
The object of the present invention is to provide a kind of can in wider pH scope, the efficient Fenton system of work and the application in occasions such as sewage disposals thereof.
In a first aspect of the present invention, provide a kind of Fenton system, described Fenton system comprises: composite cathode electrode, inert anode and electrolyte solution, and wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene.
In another preference, described metal oxide is selected from lower group: Red copper oxide, iron protoxide, Z 250 or its combination.
In another preference, the mass ratio of described Graphene and metal oxide is 10:1-1:1, is preferably 8:1-2:1, is more preferably 6:1-3:1.
In another preference, the mass ratio of described Graphene and tetrafluoroethylene is 50:1-1:1, is preferably 30:1-2:1, is more preferably 20:1-5:1.
In another preference, in described composite cathode electrode, the mass ratio of Graphene, metal oxide and tetrafluoroethylene is (5-50): (2-50): (1-5), is preferably (10-30): (3-10): (1-3).
In another preference, in described composite cathode electrode, the weight sum of Graphene, metal oxide and tetrafluoroethylene three accounts for the 90-100% of composite cathode electrode weight (wherein except sealing material (as epoxy resin)), preferably 95-100%, more preferably 98-100%, best 99-100%.
In another preference, at least one major surfaces sealing material (as epoxy resin) of described composite cathode electrode seals.
In another preference, described Graphene purity >=99wt% (as 99-99.99wt%).
In another preference, described Graphene mean diameter is 1-50 μm, is preferably 2-30 μm, more preferably about 10 ± 5 μm.
In another preference, described Graphene is selected from lower group: single-layer graphene, multi-layer graphene or its combination.
In another preference, described composite cathode electrode is of a size of 1-10cm
2, be preferably 2-8cm
2, be more preferably 3-5cm
2.
In another preference, the thickness of described composite cathode electrode is 0.5-100mm, is preferably 1-20mm, is more preferably 2-10mm.
In another preference, described inert anode is inertia noble metal electrode, is preferably platinum electrode.
In another preference, described electrolyte solution is selected from lower group: sodium sulfate, potassium sulfate, ammonium sulfate or its combination.
In another preference, described Fenton system also comprises the pending waste liquid containing pollutent, and preferably described pending waste liquid includes organic waste water.
In another preference, described organic waste water is selected from lower group: waste water from dyestuff, pharmacy waste water, sanitary sewage or its combination.
In another preference, the COD of the described pending waste liquid containing pollutent is 10-300mg/L, is preferably 100-150mg/L.
In another preference, in described Fenton system, the concentration of the pending waste liquid containing pollutent is 0.1-50g/L, and being preferably 1-40g/L, is more preferably 5-20g/L.
In another preference, the potential difference between described inert anode electrode and described composite cathode electrode is 0.5-20V/cm, is preferably 1-10V/cm.
In another preference, the distance between described inert anode electrode and described composite cathode electrode is 1-6cm, is preferably 2-5cm.
In another preference, described Fenton system also comprises additional power source.
In another preference, described impressed voltage is 1-10V, is preferably 2-6V.
In another preference, the pH scope of described Fenton system (contain or do not contain the pending waste liquid containing pollutent) is 2-11, preferably 3-10, more preferably 3.5-8.5.
In another preference, described Fenton system temperature is 5-50 DEG C, is preferably 10-40 DEG C, is more preferably 15-30 DEG C.
Second aspect present invention, provide a kind of method preparing Fenton system as described in the first aspect of the invention, described method comprises the steps:
(1) prepare described composite cathode electrode, wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene;
(2) composite cathode electrode obtained for step (1) and inert anode and electrolyte solution are assembled into Fenton system as described in the first aspect of the invention.
In another preference, described method also comprises step (3): in the described Fenton system that previous step obtains, add pending pollutent or the waste liquid containing described pollutent, be energized for some time under certain voltage, described pollutent is degraded.
In another preference, in described step (1), comprising: following electrode material is mixed, obtain the first mixture: Graphene, metal oxide, tetrafluoroethylene, emulsifying agent and C1-C6 alcoholic solvent; And described first mixture is sintered, thus obtained described composite cathode electrode.
In another preference, described step (1) comprising:
Get a certain amount of Graphene, Red copper oxide powder, tetrafluoroethylene, OP emulsifying agent and dehydrated alcohol, be mixed to form lotion, described lotion is rolled into membranaceous, be attached to metallic nickel online, suppress on a hydraulic press, obtained Graphene/Red copper oxide electrode, soaks the residual ethanol of for some time removing electrode surface and tetrafluoroethylene in acetone soln.
In another preference, described step (2) is:
Composite cathode electrode step (1) obtained is as negative electrode, and using platinized platinum as anode, take sulfate liquor as ionogen, by aerating apparatus anticathode, district carries out aeration, applies DC voltage-stabilizing simultaneously and forms heterogeneous Fenton system.
In another preference, described emulsifying agent is OP emulsifying agent.
In another preference, the consumption of described emulsifying agent is the 0.1-0.5wt% of the first mixture total weight amount, preferably 0.2-0.4wt%.
In another preference, the consumption of described C1-C6 alcoholic solvent is the 0.1-0.5wt% of the first mixture total weight amount, preferably 0.2-0.4wt%.
In another preference, the potential difference 0.5-20V/cm between described inert anode electrode and composite cathode electrode, preferably 1-10V/cm.
In another preference, the distance between described inert anode electrode and composite cathode electrode is 1-6cm, is preferably 2-5cm.
In another preference, the pH scope of described Fenton system (contain or do not contain the pending waste liquid containing pollutent) is 2-11, preferably 3-10, more preferably 3.5-8.5.
In another preference, described conduction time is 0.1-24 hour, preferably 30-360min, is preferably 60-240min.
Third aspect present invention, provides a kind of pollutant handling arrangement, comprises Fenton system as described in the first aspect of the invention and aerating apparatus.
In another preference, described aerating apparatus is used for carrying out aeration to the cathodic area of Fenton system.
In another preference, described device also comprises whipping appts.
In another preference, described device also comprises pollutant testing apparatus.
Fourth aspect present invention, provides the application of the system described in a kind of first aspect present invention, for pending pollutent or the waste liquid containing described pollutent of degrading.
In another preference, described organic waste water is selected from lower group: waste water from dyestuff, pharmacy waste water, sanitary sewage or its combination.
In another preference, the COD of the described pending waste liquid containing pollutent is 10-300mg/L, is preferably 100-150mg/L.
Fifth aspect present invention, provides a kind for the treatment of process of pollutent, and described method comprises step: adopt Fenton system as described in the first aspect of the invention to degrade pending pollutent or the waste liquid containing described pollutent.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 shows the photo of composite cathode electrode.
Fig. 2 shows the high performance liquid chromatography change curve that composite cathode electrode forms heterogeneous Fenton system degraded terramycin pharmacy waste water.
Fig. 3 shows the cyclic voltammetry curve of composite cathode electrode.
Fig. 4 shows the cycle down solution curve of composite cathode electrode.
Embodiment
The present inventor, by extensive and deep research, have unexpectedly discovered that one not only can at wide pH operated within range first, and can the heterogeneous Fenton system of the pending waste liquid containing pollutent of efficient degradation.In this Fenton system, adopt specific Graphene-metal oxide-tetrafluoroethylene composite cathode electrode, its newly-generated H
2o
2directly and metal oxide generation heterogeneous Fenton, the sewage disposal pH scope of Fenton system can be extended.Complete the present invention on this basis.
Term explanation
Unless otherwise defined, otherwise whole technology used herein and scientific terminology all have identical meanings as those skilled in the art understand usually.
As used herein, mention use in the numerical value specifically enumerated time, term " about " mean this value can from enumerate value variation no more than 1%.Such as, as used herein, statement " about 100 " comprise 99 and 101 and between whole values (such as, 99.1,99.2,99.3,99.4 etc.).
As used herein, term " contains " or " comprising (comprising) " can be open, semi-enclosed and enclosed.In other words, described term also comprise " substantially by ... form " or " by ... form ".
Electro-Fenton process
Fenton method has unique advantage when processing Persistent organic pollutants, is a kind of very promising wastewater processing technology.
Electro-Fenton process improves organic mineralization degree than common Fenton method, but still there is the low and automatic generation H of photo-quantum efficiency
2o
2the incomplete shortcoming of mechanism.The H that Electro-Fenton process utilizes electrochemical process to produce
2o
2and Fe
2+as the constant source of Fenton reagent.
Further, compared with Photo-Fenton, Electro-Fenton process has the following advantages: one is automatically produce H
2o
2mechanism more perfect; Two is cause the many factors of organic matter degradation (outside the oxygenizement of hydroxyl-removal free radical, also having anodic oxidation, electro-adsorption etc.).Due to H
2o
2cost far above Fe
2+, so automatically H will be produced by electrochemical process
2o
2mechanism introduce Fenton system there is very large practical application meaning.
Graphene
Graphene refers to sp
2the individual layer of carbon atom formation of hydridization and few lamellar carbon simple substance of no more than 10 layers, and related chemistry derivative, include but not limited to oxidation, fluorinated derivatives.Lamella size has 0.0001-10000 square micron, preferred 0.01-100 square micron.Suitable Graphene can by but be not limited to graphite physical stripping, chemical vapour deposition, graphite oxidation reduction method prepare.
Graphene purity as used herein is not particularly limited, usually its purity >=80%, preferably >=90%, more preferably >=95%; Best >=99% (as 99-99.99%).
In another preference, described Graphene is particulate state, and its particle diameter is not particularly limited.Representational mean diameter includes, but are not limited to: 1-50 μm, is preferably 2-30 μm, more preferably about 10 ± 5 μm.
In another preference, described Graphene is selected from lower group: single-layer graphene, multi-layer graphene or its combination.
Fenton system
During Fenton system energising of the present invention, there is the electrochemical reaction of identical equivalent in negative and positive two-stage, forms Fenton system degradation of contaminant.
Fenton system of the present invention comprises: composite cathode electrode, inert anode and electrolyte solution, and wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene.
In another preference, described metal oxide is selected from lower group: Red copper oxide, iron protoxide, Z 250 or its combination.
In another preference, the mass ratio of described Graphene and metal oxide is 10:1-1:1, is preferably 8:1-2:1, is more preferably 6:1-3:1.
In another preference, the mass ratio of described Graphene and tetrafluoroethylene is 50:1-1:1, is preferably 30:1-2:1, is more preferably 20:1-5:1.
In another preference, in described composite cathode electrode, the mass ratio of Graphene, metal oxide and tetrafluoroethylene is (5-50): (2-50): (1-5), is preferably (10-30): (3-10): (1-3).
In another preference, in described composite cathode electrode, the weight sum of Graphene, metal oxide and tetrafluoroethylene three accounts for the 90-100% of composite cathode electrode weight (wherein except sealing material (as epoxy resin)), preferably 95-100%, more preferably 98-100%, best 99-100%.
In another preference, at least one major surfaces sealing material (as epoxy resin) of described composite cathode electrode seals.
In another preference, described Graphene purity >=99wt% (as 99-99.99wt%).
In another preference, described Graphene mean diameter is 1-50 μm, is preferably 2-30 μm, more preferably about 10 ± 5 μm.
In another preference, described Graphene is selected from lower group: single-layer graphene, multi-layer graphene or its combination.
In another preference, described composite cathode electrode is of a size of 1-10cm
2, be preferably 2-8cm
2, be more preferably 3-5cm
2.
In another preference, the thickness of described composite cathode electrode is 0.5-100mm, is preferably 1-20mm, is more preferably 2-10mm.
In another preference, described inert anode is inertia noble metal electrode, is preferably platinum electrode.
In another preference, described electrolyte solution is selected from lower group: sodium sulfate, potassium sulfate, ammonium sulfate or its combination.
In another preference, described Fenton system also comprises the pending waste liquid containing pollutent, and preferably described pending waste liquid includes organic waste water.
In preference of the present invention, described Fenton system does not contain or substantially contains the electrode (or cathode electrode) based on graphite.In addition, in composite cathode electrode of the present invention, do not contain or substantially do not contain graphite (content≤1.0wt% as graphite), by composite cathode electrode total weight.
The preparation of Fenton system
Fenton system of the present invention mainly comprises the following steps:
(1) prepare described composite cathode electrode, wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene;
(2) composite cathode electrode obtained for step (1) and inert anode and electrolyte solution are assembled into Fenton system as described in the first aspect of the invention.
In another preference, described method also comprises step (3): in the described Fenton system that previous step obtains, add pending pollutent or the waste liquid containing described pollutent, be energized for some time under certain voltage, described pollutent is degraded.
In another preference, in described step (1), comprising: following electrode material is mixed, obtain the first mixture: Graphene, metal oxide, tetrafluoroethylene, emulsifying agent and C1-C6 alcoholic solvent; And described first mixture is sintered, thus obtained described composite cathode electrode.
In another preference, described step (1) comprising:
Get a certain amount of Graphene, Red copper oxide powder, tetrafluoroethylene, OP emulsifying agent and dehydrated alcohol, be mixed to form lotion, described lotion is rolled into membranaceous, be attached to metallic nickel online, suppress on a hydraulic press, obtained Graphene/Red copper oxide electrode, soaks the residual ethanol of for some time removing electrode surface and tetrafluoroethylene in acetone soln.
In another preference, described step (2) is:
Composite cathode electrode step (1) obtained is as negative electrode, and using platinized platinum as anode, take sulfate liquor as ionogen, by aerating apparatus anticathode, district carries out aeration, applies DC voltage-stabilizing simultaneously and forms heterogeneous Fenton system.
In another preference, described emulsifying agent is OP emulsifying agent.
In another preference, the consumption of described emulsifying agent is the 0.1-0.5wt% of the first mixture total weight amount, preferably 0.2-0.4wt%.
In another preference, the consumption of described C1-C6 alcoholic solvent is the 0.1-0.5wt% of the first mixture total weight amount, preferably 0.2-0.4wt%.
In another preference, the potential difference 0.5-20V/cm between described inert anode electrode and composite cathode electrode, preferably 1-10V/cm.
In another preference, the distance between described inert anode electrode and composite cathode electrode is 1-6cm, is preferably 2-5cm.
In another preference, the pH scope of described Fenton system (contain or do not contain the pending waste liquid containing pollutent) is 2-11, preferably 3-10, more preferably 3.5-8.5.
In another preference, described conduction time is 0.1-24 hour, preferably 30-360min, is preferably 60-240min.
Application
The present invention also provides the application of Fenton system of the present invention, is especially applied to the waste liquid of process containing pollutent.
In the present invention, described pending waste liquid is not particularly limited, and representational waste liquid includes organic waste water.Organic waste water is exactly the waste water based on organic pollutant, the COD content that papermaking leather and food service industry are discharged contains a large amount of organism such as carbohydrate, fat, albumen, Mierocrystalline cellulose in the waste water of more than 2000mg/L, if directly discharge can cause severe contamination.
Preferably, organic waste water is selected from lower group: waste water from dyestuff, pharmacy waste water, sanitary sewage or its combination.
In another preference, the concentration of described organic waste water is COD is 10-300mg/L, is preferably 100-150mg/L.
Major advantage of the present invention is:
(1) in Fenton system of the present invention, the H that negative electrode is newly-generated
2o
2can directly and metal oxide generation heterogeneous Fenton, organic waste water can be processed under acidity, neutrality and weak basic condition, do not need to carry out process in early stage to waste water, extend the pH scope of traditional F enton system dye wastewater treatment, in wastewater treatment process, can not secondary pollution be produced.
(2) good with electroconductibility, the Graphene that hydrogen-evolution overpotential is higher is that substrate cathode prepares material, is not sacrificing H
2o
2on the basis of productive rate, by variable valency metal oxide compound and Graphene compound, prepare composite cathode electrode.
(3) Graphene/Red copper oxide Electrode Operation is simple, and condition is easily controlled, and is suitable for industrial application.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number are weight percent and parts by weight.
Experiment material used in following examples and reagent all can obtain from commercially available channel if no special instructions.
Embodiment 1
The preparation of Fenton system No.1 and application thereof
Take 10g Graphene, 2gCu
2o (particle diameter 5-10 μm), add 2 " OP " emulsifying agents (purchased from Jiangsu Hai'an Petrochemical Plant), 2mL dehydrated alcohol and 0.8g tetrafluoroethylene, ultrasonic making is uniformly dispersed, until mixture forms cohesion shape lotion, lotion is rolled into the film being about 2.5mm, film is attached to up and down metallic nickel online, obtains Graphene/Red copper oxide electrode at 30MPa pressure, in acetone soln, soak 2h remove the residual ethanol of electrode surface and " OP " emulsifying agent.In infrared case, 80 DEG C of insulation 2h, make composite cathode electrode, its final size: floorage × height=1.0cm
2× 5mm.Fig. 1 is shown in by its pattern photo.Fig. 1 is the composite cathode electrode photo suppressed, and it is circular, back side epoxy sealing.
By the cathodic electrochromic compound very negative electrode prepared, platinized platinum is anode (between the two every 3cm), with the Na of 10g/L
2sO
4for supporting electrolyte, obtained Fenton system.
During work, terramycin pharmacy waste water dosage is 5g/L, and after interpolation, the pH value of system is 7.5, and Fenton system impressed voltage is controlled as 5V.
The terramycin degraded high performance liquid chromatography change curve of gained is shown in Fig. 2.The appearance time of terramycin is 3.02min.In figure, 7 curves are from top to bottom respectively untreated, the terramycin HPLC curve of process 20min, process 40min, process 60min, process 80min, process 100min, process 120min.
As can be seen from the figure, process 100min, effectively can degrade to the terramycin (pollutent) in terramycin pharmacy waste water.In addition, along with the prolongation of degradation time, the peak area of terramycin reduces gradually.After the conduction time of 120min, terramycin is almost removed completely, and the clearance of terramycin reaches more than 99%.
Embodiment 2
The preparation of Fenton system No.2 and stability test
Take 12g Graphene, 3gCu
2o, add 1 " OP " emulsifying agent, 1.5mL dehydrated alcohol and 0.9g tetrafluoroethylene, ultrasonic making is uniformly dispersed, until mixture forms cohesion shape lotion, lotion is rolled into the film being about 3mm, be attached on nickel screen, obtain Graphene/Red copper oxide electrode at 30MPa pressure, in acetone soln, soak 2h remove the residual ethanol of electrode surface and " OP " emulsifying agent.In infrared case, 80 DEG C of insulation 2h, namely make composite cathode electrode, its final size: floorage × height=1.0cm
2× 6mm.
In order to detect the electrocatalysis stability of this composite cathode electrode, by the cathodic electrochromic compound very negative electrode prepared, platinized platinum is anode, and saturated calomel electrode is reference electrode, with the Na of 10g/L
2sO
4for supporting electrolyte, CHI660E electrochemical workstation is adopted to carry out cyclic voltammetry scan to this composite cathode electrode.
The cyclic voltammetry curve obtained is shown in Fig. 3.Composite cathode electrode is after scan round 8 times, and the cyclic voltammetry curve of composite cathode electrode is basically identical, and redox peak does not offset, and this composite cathode electrode stable in properties in electrolytic process is described.This shows, Fenton system of the present invention has high stability.
Embodiment 3
The preparation of Fenton system No.3 and application thereof
Take 13g Graphene, 1.8gCu
2o, add 2 " OP " emulsifying agents, 1.5mL dehydrated alcohol and 1.0g tetrafluoroethylene, ultrasonic making is uniformly dispersed, until mixture forms cohesion shape lotion, lotion is rolled into the film being about 2.5mm, be attached on nickel screen, obtain Graphene/Red copper oxide electrode at 30MPa pressure, in acetone soln, soak 2h remove the residual ethanol of electrode surface and " OP " emulsifying agent.In infrared case, 80 DEG C of insulation 2h, namely make composite cathode electrode, its final size: floorage × height=1.0cm
2× 5mm.
By the cathodic electrochromic compound very negative electrode prepared, platinized platinum is anode (interval 3cm), with the Na of 10g/L
2sO
4for supporting electrolyte, pH value is 7.5, and rhdamine B waste water dosage is 5g/L, and Fenton system impressed voltage is controlled as 4V, carries out the circulation degraded test of composite cathode electrode.Degraded adds useless rhdamine B waste water after once circulating again.
The kinetic curve of cycle degradation experiment as shown in Figure 4.Result shows, composite cathode electrode circulates after 5 times, and kinetic curve is almost completely the same, and this points out Fenton system of the present invention after repeatedly circulation, still has good electro catalytic activity.
In addition, A/A
0ratio shows, processes through the conduction time of 180min, all reaches 99.8% or higher in each process to the clearance of rhdamine B.
Embodiment 4
The preparation of Fenton system No.4 and application thereof
Take 8g Graphene, 1.5gCu
2o, add 2 " OP " emulsifying agents, 1.5mL dehydrated alcohol and 0.7g tetrafluoroethylene, ultrasonic making is uniformly dispersed, until mixture forms cohesion shape lotion, lotion is rolled into the film being about 2.0mm, be attached on nickel screen, obtain Graphene/Red copper oxide electrode at 30MPa pressure, in acetone soln, soak 2h remove the residual ethanol of electrode surface and " OP " emulsifying agent.In infrared case, 80 DEG C of insulation 2h, namely make cathode electrode, its final size: floorage × height=1.0cm
2× 4mm.
With embodiment 1, by the cathodic electrochromic compound very negative electrode prepared, platinized platinum is anode, with the Na of 10g/L
2sO
4for supporting electrolyte, organic dye acid brilliant pink waste water dosage is 6g/L (final concentration), and pH value is 6.5, and Fenton system impressed voltage is 5V respectively.
Result shows, after 120min processes conduction time, to the clearance of acid brilliant pink reach >=95%.
Embodiment 5
The preparation of Fenton system No.5 and application thereof
According to method as described in Example 1, prepare Fenton system No.5, difference is: change Red copper oxide into Z 250.
Result shows, within the conduction time of 120min, reaches more than 98% to the clearance of terramycin.
Comparative example 1
The preparation of Fenton system No.C1 and application thereof
According to method as described in Example 3, prepare Fenton system No.C1, difference is: replace 13g Graphene with 13g graphite.
Carry out the degradation experiment of rhdamine B waste water with embodiment 3, when the pH value of Fenton system is 7.5 (with embodiment 3), in identical 180min degradation time, this graphite composite cathode electrode is 82.5% to the degradation rate of 5g/L rhodamine B.(in embodiment 3, Graphene composite cathode electrode is 99.8% to the degradation rate of 5g/L rhodamine B).
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a Fenton system, is characterized in that, described Fenton system comprises: composite cathode electrode, inert anode and electrolyte solution, and wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene.
2. Fenton system as claimed in claim 1, it is characterized in that, described metal oxide is selected from lower group: Red copper oxide, iron protoxide, Z 250 or its combination.
3. Fenton system as claimed in claim 1, it is characterized in that, the mass ratio of described Graphene and metal oxide is 10:1-1:1, is preferably 8:1-2:1, is more preferably 6:1-3:1.
4. Fenton system as claimed in claim 1, it is characterized in that, the mass ratio of described Graphene and tetrafluoroethylene is 50:1-1:1, is preferably 30:1-2:1, is more preferably 20:1-5:1.
5. Fenton system as claimed in claim 1, is characterized in that, in described Fenton system, the concentration of the pending waste liquid containing pollutent is 0.1-50g/L, and being preferably 1-40g/L, is more preferably 5-20g/L.
6. Fenton system as claimed in claim 1, is characterized in that, the pH scope of described Fenton system (contain or do not contain the pending waste liquid containing pollutent) is 2-11, preferably 3-10, more preferably 3.5-8.5.
7. prepare a method for Fenton system as claimed in claim 1, it is characterized in that, described method comprises the steps:
(1) prepare described composite cathode electrode, wherein, described composite cathode electrode contains Graphene, metal oxide and tetrafluoroethylene;
(2) composite cathode electrode obtained for step (1) and inert anode and electrolyte solution are assembled into Fenton system as claimed in claim 1.
8. a pollutant handling arrangement, is characterized in that, comprises Fenton system as claimed in claim 1 and aerating apparatus.
9. with an application for system according to claim 1, it is characterized in that, for pending pollutent or the waste liquid containing described pollutent of degrading.
10. a treatment process for pollutent, is characterized in that, described method comprises step: adopt Fenton system as claimed in claim 1 to degrade pending pollutent or containing the waste liquid of described pollutent.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006857A (en) * | 2016-07-12 | 2016-10-12 | 中国石油化工股份有限公司 | Method for degrading organic dye wastewater through graphene electrode and photoelectric Feton cooperatively |
| CN106045003A (en) * | 2016-07-12 | 2016-10-26 | 中国石油化工股份有限公司 | Method for treating organic dyestuff wastewater with heterogeneous electric Fenton system |
| CN106139933A (en) * | 2016-06-24 | 2016-11-23 | 辽宁科技学院 | A kind of preparation method of reactive electrochemical cathode film |
| CN107008156A (en) * | 2017-04-21 | 2017-08-04 | 中国科学院生态环境研究中心 | Graphene filtering composite membrane and preparation method thereof |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN107649181A (en) * | 2017-08-30 | 2018-02-02 | 北京工业大学 | The preparation and application of a kind of heterogeneous fenton catalyst of support type based on teflon-coated |
| CN110559853A (en) * | 2019-09-30 | 2019-12-13 | 华中师范大学 | Method and device for removing gaseous pollutants by anode and cathode synchronous electrochemical method |
| CN112744972A (en) * | 2020-12-31 | 2021-05-04 | 中国科学院生态环境研究中心 | Device and method for water treatment by cooperation of electro-Fenton-membrane distillation |
| CN113044930A (en) * | 2021-03-19 | 2021-06-29 | 西安建筑科技大学 | Tannic acid heterogeneous synergistic electro-Fenton method for catalytic degradation of phenolic organic wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789150A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Method and apparatus for highly efficient removal of water organisms by utilizing photoelectric Fenton reaction |
| CN101645515A (en) * | 2009-08-20 | 2010-02-10 | 华南理工大学 | Microbiological fuel cell as well as preparation method and applications thereof |
| CN102633322A (en) * | 2012-04-17 | 2012-08-15 | 西安建筑科技大学 | Semi-coke waste water pretreatment method based on Electro-Fenton oxidization technology |
| CN102659223A (en) * | 2012-05-28 | 2012-09-12 | 南京工业大学 | Photo/electricity Fenton device for treating refractory organic wastewater |
| CN104710057A (en) * | 2015-01-22 | 2015-06-17 | 华北电力大学 | Papermaking wastewater treatment apparatus |
-
2015
- 2015-11-13 CN CN201510780799.5A patent/CN105417638A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789150A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Method and apparatus for highly efficient removal of water organisms by utilizing photoelectric Fenton reaction |
| CN101645515A (en) * | 2009-08-20 | 2010-02-10 | 华南理工大学 | Microbiological fuel cell as well as preparation method and applications thereof |
| CN102633322A (en) * | 2012-04-17 | 2012-08-15 | 西安建筑科技大学 | Semi-coke waste water pretreatment method based on Electro-Fenton oxidization technology |
| CN102659223A (en) * | 2012-05-28 | 2012-09-12 | 南京工业大学 | Photo/electricity Fenton device for treating refractory organic wastewater |
| CN104710057A (en) * | 2015-01-22 | 2015-06-17 | 华北电力大学 | Papermaking wastewater treatment apparatus |
Non-Patent Citations (4)
| Title |
|---|
| 刘栓 等: "Fe3O4@Graphite电极中性条件下电Fenton降解有机污染物", 《环境化学》 * |
| 刘栓 等: "电(类)Fenton体系阴极材料的研究进展", 《三峡大学学报（自然科学版）》 * |
| 刘钥 等: "《水处理高级氧化技术及工程应用》", 31 August 2014 * |
| 林恒 等: "电-Fenton及类电-Fenton技术处理水中有机污染物", 《化学进展》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106139933B (en) * | 2016-06-24 | 2019-03-22 | 辽宁科技学院 | A kind of preparation method of reactivity electrochemical cathode film |
| CN106139933A (en) * | 2016-06-24 | 2016-11-23 | 辽宁科技学院 | A kind of preparation method of reactive electrochemical cathode film |
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| CN107008156B (en) * | 2017-04-21 | 2019-12-03 | 中国科学院生态环境研究中心 | Graphene filters composite membrane and preparation method thereof |
| CN107324454A (en) * | 2017-07-07 | 2017-11-07 | 重庆三峡学院 | A kind of graphene aerogel electrode material for loading copper ion and preparation method thereof |
| CN107324454B (en) * | 2017-07-07 | 2020-12-15 | 重庆三峡学院 | Copper ion-loaded graphene aerogel electrode material and preparation method thereof |
| CN107649181A (en) * | 2017-08-30 | 2018-02-02 | 北京工业大学 | The preparation and application of a kind of heterogeneous fenton catalyst of support type based on teflon-coated |
| CN110559853A (en) * | 2019-09-30 | 2019-12-13 | 华中师范大学 | Method and device for removing gaseous pollutants by anode and cathode synchronous electrochemical method |
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