CN107601624B - Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers - Google Patents
Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers Download PDFInfo
- Publication number
- CN107601624B CN107601624B CN201711019400.7A CN201711019400A CN107601624B CN 107601624 B CN107601624 B CN 107601624B CN 201711019400 A CN201711019400 A CN 201711019400A CN 107601624 B CN107601624 B CN 107601624B
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- carbon fiber
- electro
- cathode
- fenton
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 29
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 20
- 229960001680 ibuprofen Drugs 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000297 Rayon Polymers 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000003814 drug Substances 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229960002413 ferric citrate Drugs 0.000 description 12
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000007832 Na2SO4 Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical class [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000820 nonprescription drug Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000955 prescription drug Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method and application of an electro-Fenton cathode material based on a supported activated carbon fiber. The preparation method of the activated carbon fiber electro-Fenton cathode is simple, the conditions are mild, and the danger possibly generated during transportation and storage is avoided by generating the hydrogen peroxide in situ; the treatment process is clean, and Fe (II) medicament does not need to be continuously added outside, so that the sludge yield is reduced, and secondary pollution is not generated. The invention has the advantages of cheap and easily obtained raw materials, simple preparation method, short treatment period, easy combination with other treatment methods and contribution to large-scale production and comprehensive treatment of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and electrochemical water treatment, relates to a heterogeneous electro-Fenton activated carbon fiber cathode, and particularly relates to preparation and application of an electro-Fenton cathode material based on load-type activated carbon fibers.
Background
With economic development and social progress, a wide variety of drugs and personal care products (PPCPs), including prescription drugs and non-prescription drugs, veterinary drugs, cosmetics, artificially synthesized musk, hair dyes, bactericides and the like, are discharged into the water environment, and such novel pollutants are usually easy to be biologically enriched, affect aquatic organisms at low concentrations, and further affect human health. Most PPCPs are discharged into wastewater in raw or converted form into wastewater treatment plants. At present, for the sewage containing trace amount of pollutants difficult to degrade, the sewage is not available at home and abroadAn economical and effective method which can be widely popularized. The electro-Fenton process, as an environmentally friendly advanced oxidation technology for water treatment, draws increasing attention in the treatment of refractory organic pollutants. Since it can generate H in situ2O2Effectively avoiding the danger of transportation and storage. Traditional homogeneous phase electro-Fenton technique is more harsh to pH requirement, is only applicable to at present and handles acidic waste water (pH 2 ~ 4), to neutral and alkaline waste water, need throw with a large amount of acid, alkaline medicament before handling and discharging, greatly increased treatment cost, still can produce a large amount of iron-containing sludge after the reaction, cause secondary pollution.
Due to the above limitations of the homogeneous electro-Fenton system, the research and development of the non-homogeneous electro-Fenton catalyst has been the focus of domestic and foreign research. In patent CN 105905985 a, a decontaminated graphite felt material is used as a cathode, a platinum wire is used as an anode, a saturated calomel electrode is used as a reference electrode, a graphene oxide suspension, 3-4-ethylenedioxythiophene and sodium poly-p-styrenesulfonate mixed solution is used as an electrolyte, and a cyclic voltammetry electropolymerization method is adopted to prepare a modified graphite felt heterogeneous electro-fenton electrode; in patent CN 103496764A, a high oxygen evolution overpotential electrode is used as an anode, an air diffusion electrode is used as a cathode, and polytetrafluoroethylene modified iron-carbon is used as a heterogeneous catalyst to treat dichlorophenol, and the effect of the PTFE-bonded air diffusion electrode on pressure resistance and amplification experiments is yet to be examined.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of an electro-Fenton cathode material based on a supported activated carbon fiber.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the electro-Fenton cathode material based on the supported activated carbon fiber comprises the following steps:
(1) pretreating an activated carbon fiber cathode substrate material;
(2) sequentially dipping the pretreated material in a complexing agent and a metal salt solution;
(3) and (5) washing and drying for later use.
The active carbon fiber cathode substrate material is viscose-based active carbon fiber, phenolic-based active carbon fiber, pitch-based active carbon fiber or polyacrylonitrile-based active carbon fiber.
The pretreatment is to ultrasonically soak the glass fiber for 10-30 minutes by using acetone or absolute ethyl alcohol, ultrasonically soak the glass fiber for 10-30 minutes by using 1-3 mol/L nitric acid solution after cleaning, finally clean the glass fiber by using deionized water, and dry the glass fiber for later use.
The complexing agent is one or more of ethylenediamine tetraacetic acid, succinic acid, oxalic acid, oxalate, citric acid and citrate; the metal salt is copper salt and/or iron salt.
And sequentially soaking the pretreated material in a complexing agent for 1-6 h and a metal salt solution for 1-6 h at normal temperature.
In an electro-Fenton system, the electro-Fenton cathode material is used as a cathode, dissolved oxygen in water is reduced on the surface of activated carbon fiber to generate hydrogen peroxide, and the obtained hydrogen peroxide reacts with a metal ion complex loaded on the surface of the activated carbon fiber to generate hydroxyl radicals, so that organic pollutants are degraded through oxidation.
The dissolved oxygen in the water is reduced on the surface of the cathode of the activated carbon fiber to generate hydrogen peroxide under the environmental conditions that: the pH is 2-10, and the temperature is 20-90 ℃.
In the electro-Fenton system, platinum, graphite, boron-doped diamond or metal oxide (RuO)2/Ti、IrO2/Ti、PbO2/Ti or SnO2and/Ti) is an anode.
The electro-Fenton cathode material and a counter electrode can also form an electrolytic cell, and the water flow state is static or flowing and is 0-20 mA/cm2And does not include 0mA/cm2The electrolytic reaction is carried out at a current density.
In the application system of the invention, air or oxygen is injected into the cathode region, or the oxygen generated by electrolyzing water at the anode is utilized to generate hydrogen peroxide in situ.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the conventional heterogeneous Fenton reagent, the method does not need to add hydrogen peroxide externally, effectively avoids the dangers of the reagent in the aspects of transportation and storage, and can control the yield of the hydrogen peroxide and the degradation rate of organic matters by controlling current and voltage.
2. The method adopts the activated carbon fiber as the cathode, has the characteristics of adsorption, conductivity, high specific surface area and the like, has the property of a quasi-three-dimensional electrode, increases the electrode surface of unit cell volume, and improves the current efficiency and the treatment effect.
3. According to the method, the iron ion or copper ion complex is loaded on the surface of the carbon material cathode, hydrogen peroxide can be effectively catalytically decomposed within the range of pH 2-10 to generate hydroxyl radicals, the defects of narrow pH application range and large iron sludge production amount in the traditional Fenton technology are overcome, and the method has good economic, environmental and social benefits.
Drawings
Fig. 1 is a schematic diagram of the application of the present invention.
Fig. 2 is a scanning electron microscope picture of the activated carbon fiber loaded with ferric citrate of the present invention.
Fig. 3 is a schematic diagram showing the comparison of the effects of activated carbon fiber adsorption, activated carbon fiber energization, activated carbon fiber loaded ferric citrate (heterogeneous), activated carbon fiber + ferric citrate (homogeneous), and activated carbon fiber + ferrous sulfate (homogeneous) on ibuprofen removal.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
The invention relates to a preparation method of an electro-Fenton cathode material based on load-type activated carbon fibers, which comprises the following steps:
(1) pretreatment: the method comprises the steps of taking viscose-based activated carbon fibers, phenolic-based activated carbon fibers, asphalt-based activated carbon fibers or polyacrylonitrile-based activated carbon fibers as an activated carbon fiber cathode substrate material, ultrasonically soaking the activated carbon fiber cathode substrate material for 10-30 minutes by using acetone or absolute ethyl alcohol, ultrasonically soaking the activated carbon fiber cathode substrate material for 10-30 minutes by using 1-3 mol/L nitric acid solution after cleaning, finally cleaning the activated carbon fiber cathode substrate material by using deionized water, and drying the cleaned activated carbon fiber cathode substrate material for later use.
(2) Sequentially dipping the pretreated material in a complexing agent and a metal salt solution; the complexing agent can be one or more of ethylenediamine tetraacetic acid, succinic acid, oxalic acid, oxalate, citric acid and citrate; the metal salt is copper salt and/or iron salt. The activated carbon fiber is sequentially soaked in the complexing agent for 1-6 h and the metal salt solution for 1-6 h, and the two steps of soaking are carried out at normal temperature.
(3) Washing with deionized water, and drying for use.
Fig. 1 is a schematic diagram of the application of the present invention. The dissolved oxygen in the water is electrochemically and rapidly reduced on the surface of the cathode to generate hydrogen peroxide in situ, the hydrogen peroxide and the iron ion complex loaded on the surface of the carbon cathode are excited to react to generate hydroxyl radicals, and the ibuprofen is oxidatively degraded.
Fig. 2 is a scanning electron microscope image of the activated carbon fiber loaded with the ferric citrate complex, and ferric citrate complex particles are distributed on the smooth surface of the activated carbon fiber.
As shown in FIG. 3, the electro-Fenton cathode material obtained by the invention is used in an electro-Fenton system, and platinum, graphite, boron-doped diamond or metal oxide (RuO)2/Ti、IrO2/Ti、PbO2/Ti or SnO2and/Ti) is used as an anode, the dissolved oxygen in the water is reduced on the surface of the activated carbon fiber to generate hydrogen peroxide, and the obtained hydrogen peroxide reacts with the metal ion complex loaded on the surface of the activated carbon fiber to generate hydroxyl radicals to oxidize and degrade organic pollutants.
Fig. 3 shows a schematic diagram comparing the effects of adsorption by activated carbon fiber, electrification of activated carbon fiber, loading of activated carbon fiber with ferric citrate (heterogeneous), activated carbon fiber + ferric citrate (homogeneous), and activated carbon fiber + ferrous sulfate (homogeneous) on ibuprofen removal. It can be seen that the removal of ibuprofen by activated carbon fiber adsorption and electrification (reduction of oxygen to produce hydrogen peroxide) is not high, while heterogeneous electro-fenton shows good ibuprofen removal rate under pH near-neutral condition, which is equivalent to the removal rate of ibuprofen by homogeneous electro-fenton at pH 3 of 120 min. The active carbon fiber is loaded with ferric citrate (heterogeneous), namely a ferric citrate complex is loaded on the surface of the active carbon fiber; activated carbon fiber + ferric citrate (homogeneous phase), which means that the ferric citrate is dissolved in a solution to be treated; activated carbon fiber + ferrous sulfate (homogeneous), which means that ferrous sulfate is dissolved in the solution to be treated.
Example 1 gives the formation of hydrogen peroxide and hydroxyl radicals during the electro-fenton reaction:
volume of reaction solution: 250mL of high purity water
Temperature of the reaction solution: 30 +/-2 DEG C
Initial pH of reaction solution: 6.8
Electrode area: 15cm2(2.5cm×6cm)
Electrolyte concentration: 0.05M Na2SO4
Oxygen flow rate: 100mL/min
Current intensity: 0.05A
Reaction time: 30min,60min,90min,120min
TABLE 1 concentration of generated oxides
| Concentration of generated oxide | 30min | 60min | 90min | 120min |
| Hydrogen peroxide concentration (μ M) | 104.7 | 141.8 | 163.2 | 182.7 |
| Hydroxyl radical concentration (μ M) | 8.6 | 13.7 | 20.6 | 26.1 |
As can be seen from example 1, the concentration of the generated hydrogen peroxide and hydroxyl radicals increases with increasing reaction time, indicating that this method is effective in exciting hydrogen peroxide to generate strong oxidant hydroxyl radicals under pH neutral conditions.
Example 2 illustrates the removal of ibuprofen of different initial concentrations according to the invention
Volume of reaction solution: 250mL of high purity water
Temperature of the reaction solution: 30 +/-2 DEG C
Initial pH of reaction solution: 6.8
Electrode area: 15cm2(2.5cm×6cm)
Electrolyte concentration: 0.05M Na2SO4
Oxygen flow rate: 100mL/min
Current intensity: 0.05A
Reaction time: 120min
Initial concentration: 1mg/L,5mg/L,10mg/L,20mg/L
Table 2 removal of ibuprofen for different initial concentrations
| Initial concentration (mg/L) | 1 | 5 | 10 | 20 |
| Removal Rate (%) | 98.0 | 97.5 | 96.8 | 94.7 |
As can be seen from example 2, the removal was relatively good for both the low and high concentrations of ibuprofen, 1mg/L to 20mg/L, and greater than 95% for the initial concentration of ibuprofen less than 10 mg/L.
Example 3 shows the effect of different current densities on the ibuprofen removal
Volume of reaction solution: 250mL of high purity water
Temperature of the reaction solution: 30 +/-2 DEG C
Initial pH of reaction solution: 6.8
Initial ibuprofen concentration: 10mg/L
Electrode area: 15cm2(2.5cm×6cm)
Electrolyte concentration: 0.05M Na2SO4
Oxygen flow rate: 100mL/min
Current intensity: 0.05A
Reaction time: 120min
Initial concentration: 1mA/cm2,3mA/cm2,5mA/cm2,7mA/cm2
Table 3 ibuprofen removal at different current densities
| Current Density (mA/cm)2) | 1 | 3 | 5 | 7 |
| Removal Rate (%) | 89.8 | 94.3 | 96.8 | 97.1 |
As can be seen from example 3, the removal of ibuprofen increases with increasing current density, which is higher than 5mA/cm2The removal rate of ibuprofen is not very different.
Example 4 shows the effect of different run cycles on the ibuprofen removal
Volume of reaction solution: 250mL of high purity water
Temperature of the reaction solution: 30 +/-2 DEG C
Initial pH of reaction solution: 6.8
Initial ibuprofen concentration: 10mg/L
Electrode area: 15cm2(2.5cm×6cm)
Electrolyte concentration: 0.05M Na2SO4
Oxygen flow rate: 100mL/min
Current intensity: 0.05A
One cycle is as follows: 120min
Table 4 different run cycles for ibuprofen removal
| Period of operation | 1 | 2 | 3 | 4 | 5 | 6 |
| Removal Rate (%) | 96.7 | 90.6 | 90.7 | 88.8 | 87.4 | 85.3 |
It can be seen from example 4 that, after 6 operating cycles (12 hours), ibuprofen is still well removed (more than 85%), the removal efficiency of the electrode on organic pollutants can be improved by re-loading ferric citrate subsequently, the loading process is mild in condition, short in time and good in application prospect.
In summary, the invention utilizes the electro-Fenton cathode material based on the supported activated carbon fiber, the dissolved oxygen generates hydrogen peroxide on the surface of the cathode of the activated carbon fiber through the oxygen reduction reaction of two electrons, the generated hydrogen peroxide reacts with the iron ion or copper ion complex catalyst loaded on the surface of the activated carbon fiber to generate strong oxidant hydroxyl radical, and the organic matters which are difficult to degrade can be removed by oxidation under the condition of neutral pH. The preparation method of the activated carbon fiber electro-Fenton cathode is simple, the conditions are mild, and the danger possibly generated during transportation and storage is avoided by generating the hydrogen peroxide in situ; the treatment process is clean, and Fe (II) medicament does not need to be continuously added outside, so that the sludge yield is reduced, and secondary pollution is not generated. The invention has the advantages of cheap and easily obtained raw materials, simple preparation method, short treatment period, easy combination with other treatment methods and contribution to large-scale production and comprehensive treatment of organic pollutants. The application of the method is a method for treating the electro-Fenton wastewater, which can continuously add the ferric salt, has wide pH application range, is particularly suitable for the electro-Fenton wastewater under the near-neutral condition, and has great application prospect.
Claims (7)
1. The preparation method of the electro-Fenton cathode material based on the supported activated carbon fiber is characterized by comprising the following steps of:
(1) taking an activated carbon fiber cathode substrate material for pretreatment, wherein the pretreatment comprises the steps of ultrasonically soaking the activated carbon fiber cathode substrate material by using acetone or absolute ethyl alcohol, ultrasonically soaking the activated carbon fiber cathode substrate material by using a nitric acid solution after cleaning, and finally cleaning and drying the activated carbon fiber cathode substrate material for later use;
(2) sequentially soaking the pretreated material in a complexing agent for 1-6 hours and a metal salt solution for 1-6 hours at normal temperature, wherein the complexing agent is one or more of ethylenediamine tetraacetic acid, succinic acid, oxalic acid, oxalate, citric acid and citrate; the metal salt is copper salt and/or iron salt;
(3) and (5) washing and drying for later use.
2. The preparation method of the electro-Fenton cathode material based on the supported activated carbon fiber according to claim 1, wherein the activated carbon fiber cathode base material is viscose-based activated carbon fiber, phenolic-based activated carbon fiber, pitch-based activated carbon fiber or polyacrylonitrile-based activated carbon fiber.
3. The use of the electro-Fenton cathode material based on supported activated carbon fibers as claimed in claim 1, wherein in the electro-Fenton system, the electro-Fenton cathode material is used as a cathode, dissolved oxygen in water is reduced on the surface of the activated carbon fibers to generate hydrogen peroxide, and the obtained hydrogen peroxide reacts with the metal ion complex loaded on the surface of the activated carbon fibers to generate hydroxyl radicals, so as to oxidatively degrade the organic pollutant which is ibuprofen.
4. The use of claim 3, wherein the dissolved oxygen in the water is reduced on the cathode surface of the activated carbon fiber to generate hydrogen peroxide under the following environmental conditions: the pH is 2-10, and the temperature is 20-90 ℃.
5. Use according to claim 3, wherein the electro-Fenton system is anodised by platinum, graphite, boron-doped diamond or a metal oxide.
6. The use of claim 3, wherein the electro-Fenton cathode material and the counter electrode are combined to form an electrolytic cell, and the water flow state is static or flowing and is 0-20 mA/cm2And does not include 0mA/cm2The electrolytic reaction is carried out at a current density.
7. Use according to claim 6, wherein hydrogen peroxide is generated in situ by injection of air or oxygen in the cathode region or by oxygen generated by electrolysis of water at the anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711019400.7A CN107601624B (en) | 2017-10-26 | 2017-10-26 | Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711019400.7A CN107601624B (en) | 2017-10-26 | 2017-10-26 | Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107601624A CN107601624A (en) | 2018-01-19 |
| CN107601624B true CN107601624B (en) | 2020-10-27 |
Family
ID=61080928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711019400.7A Active CN107601624B (en) | 2017-10-26 | 2017-10-26 | Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107601624B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282704B (en) * | 2019-05-07 | 2022-03-04 | 广东省测试分析研究所（中国广州分析测试中心） | Electrochemical modified filler for water treatment |
| CN110240250A (en) * | 2019-06-06 | 2019-09-17 | 南京融众环境工程研究院有限公司 | A kind of method of degrading decabromodiphenyl ether |
| CN110228838A (en) * | 2019-06-19 | 2019-09-13 | 南开大学 | A kind of RGO/MoS2/Ce0.75Zr0.25O2Cathode material and its preparation method and application |
| CN110342615A (en) * | 2019-06-21 | 2019-10-18 | 同济大学 | A kind of electrode material suitable for electric Fenton degradation of contaminant, preparation method and application |
| CN110963637A (en) * | 2019-10-27 | 2020-04-07 | 平湖石化有限责任公司 | Biochemical treatment method for acrylic acid and ester production wastewater |
| CN111054341A (en) * | 2020-01-10 | 2020-04-24 | 北京工业大学 | Preparation method and application of bimetal oxide loaded activated carbon fiber composite electrode |
| CN111422953A (en) * | 2020-04-01 | 2020-07-17 | 北京林业大学 | In-situ flocculation-Fenton coupling electrochemical method for advanced treatment of high-salinity wastewater |
| CN112408555B (en) * | 2020-11-14 | 2022-11-15 | 北京工业大学 | Preparation and application of cuprous oxide/carbon nanotube/copper foam composite electrode for heterogeneous electro-Fenton system |
| CN112811529B (en) * | 2021-01-13 | 2023-01-10 | 中科南京绿色制造产业创新研究院 | Graphene-based heterogeneous electrocatalytic cathode and preparation method and application thereof |
| CN113045063B (en) * | 2021-03-17 | 2022-07-22 | 清华大学 | Water purifying device and method based on self-driven electrochemical Fenton-like flocculation reaction |
| CN113149350A (en) * | 2021-04-15 | 2021-07-23 | 北京京华清源环保科技有限公司 | Chelated biological catalytic particles for in-situ restoration of water body and preparation method thereof |
| CN113371892B (en) * | 2021-05-28 | 2022-05-17 | 广东工业大学 | Method for removing heavy metals in wastewater by electrochemical method |
| CN114108009B (en) * | 2021-06-30 | 2024-02-23 | 中山大学 | Method for preparing and activating hydrogen peroxide in situ based on water oxidation and application thereof |
| CN114534726B (en) * | 2022-03-09 | 2024-05-03 | 浙江工业大学 | Iron/oxygen doped carbon-based filtering type electro-Fenton cathode and preparation method and application thereof |
| CN115382530A (en) * | 2022-08-23 | 2022-11-25 | 南京工业大学 | Catalyst for strengthening homogeneous Fenton oxidation synergistic adsorption and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092820A (en) * | 2011-01-04 | 2011-06-15 | 华中师范大学 | Method and device for removing organic matters from water by using double-pool double-effect visible light in response to photo-electro-Fenton reaction |
| CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN104229949A (en) * | 2014-09-18 | 2014-12-24 | 西安建筑科技大学 | Preparation and application of iron ion and manganese ion loaded activated carbon fiber composite cathode |
| CN104386784A (en) * | 2014-09-18 | 2015-03-04 | 西安建筑科技大学 | Iron ion loaded activated carbon fiber composite cathode, preparation method and application thereof |
-
2017
- 2017-10-26 CN CN201711019400.7A patent/CN107601624B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102092820A (en) * | 2011-01-04 | 2011-06-15 | 华中师范大学 | Method and device for removing organic matters from water by using double-pool double-effect visible light in response to photo-electro-Fenton reaction |
| CN102909073A (en) * | 2012-10-12 | 2013-02-06 | 浙江理工大学 | Preparation method and application of heterogeneous Fenton-like catalyst |
| CN104229949A (en) * | 2014-09-18 | 2014-12-24 | 西安建筑科技大学 | Preparation and application of iron ion and manganese ion loaded activated carbon fiber composite cathode |
| CN104386784A (en) * | 2014-09-18 | 2015-03-04 | 西安建筑科技大学 | Iron ion loaded activated carbon fiber composite cathode, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107601624A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107601624B (en) | Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers | |
| CN109896598B (en) | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water | |
| Xu et al. | Simultaneous electricity generation and wastewater treatment in a photocatalytic fuel cell integrating electro-Fenton process | |
| CN103435134B (en) | A kind of based on CNTs/Fe 3o 4three-dimensional electricity-Fenton improves the method for blue charcoal wastewater biodegradability | |
| CN102633322B (en) | Semi-coke waste water pretreatment method based on Electro-Fenton oxidization technology | |
| CN111167513B (en) | Flexible electro-catalytic membrane for removing nitrate in water and preparation method and application thereof | |
| CN201567249U (en) | Ultrasonic electrochemical wastewater treatment device | |
| CN102211830B (en) | Method for treating cutting liquid wastewater by electro-catalytic oxidation | |
| CN112811678B (en) | Improved double-cathode non-aeration electro-Fenton sewage treatment device and method | |
| CN103641212A (en) | Method for preparing graphite felt cathode material for treating organic wastewater | |
| CN108017120A (en) | A kind of method using Novel anode electrocatalytic oxidation processing phenol organic wastewater | |
| CN111217429A (en) | Method for efficiently removing organic wastewater by molybdenum disulfide-assisted catalysis of heterogeneous electro-Fenton of zero-valent iron | |
| CN107200384A (en) | A kind of carbon fiber electrode preparation method of efficient production hydrogen peroxide treatment organic wastewater | |
| Xu et al. | Electrogeneration of hydrogen peroxide by oxygen reduction using anodized graphite felt | |
| CN106904728B (en) | Light-driven wastewater denitrification method | |
| CN113184951B (en) | Modification method and application of graphite felt cathode in electric over-ozonation system | |
| CN108706689A (en) | A kind of method of the preparation method and wastewater treatment of electrode material | |
| CN112723494A (en) | Water treatment technology for promoting synchronous removal of refractory organic matters and nitrogen elements by electro-activated persulfate | |
| CN108751378B (en) | Fe3O4Ag @ Si three-dimensional composite electrode, preparation method thereof and advanced oxidation integration technology system | |
| CN110194519B (en) | Method for efficiently removing 1, 4-dioxane by pulse electro-Fenton | |
| CN113213589B (en) | Three-metal carbon nanofiber loaded electro-Fenton cathode and preparation method and application thereof | |
| CN215208628U (en) | Flow type electrochemical system for generating double oxidants through cooperation of double electrodes | |
| CN113003668B (en) | Method for synchronously removing PPCPs (pentatricopeptide repeats) by inactivating urine by using singlet oxygen generated in situ by three-dimensional electrochemical reactor | |
| CN114426320A (en) | Preparation method of FeOCl/nitrogen-phosphorus self-doped biochar cathode and application of FeOCl/nitrogen-phosphorus self-doped biochar cathode in sewage treatment | |
| CN108383214B (en) | Photovoltaic electro-catalysis organic wastewater treatment reactor and anode preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |