CN104386784A - Iron ion loaded activated carbon fiber composite cathode, preparation method and application thereof - Google Patents
Iron ion loaded activated carbon fiber composite cathode, preparation method and application thereof Download PDFInfo
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- CN104386784A CN104386784A CN201410479317.8A CN201410479317A CN104386784A CN 104386784 A CN104386784 A CN 104386784A CN 201410479317 A CN201410479317 A CN 201410479317A CN 104386784 A CN104386784 A CN 104386784A
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to an iron ion loaded activated carbon fiber composite cathode, a preparation method and application thereof. The composite cathode includes iron ion loaded activated carbon fiber. The iron ion loaded activated carbon fiber composite cathode is applied to treatment of humic acid-containing wastewater and triphenylmethane dyes in printing and dyeing wastewater by an Electro-Fenton technique. The method for preparation of the iron ion loaded activated carbon fiber composite cathode includes an inner layer adsorption process and a precipitation process. Iron ions are loaded on activated carbon fiber, the treatment process is simplified, production of sludge is completely eradicated, and no secondary pollution exists; the iron ions loaded on the activated carbon fiber can react with H2O2 generated by electroreduction of dissolved oxygen on the composite cathode surface, thus reinforcing reaction on the composite cathode surface and strengthening the reaction efficiency; iron ions and acidic groups on the surface of the activated carbon fiber undergo inner layer adsorption, so that the iron ions are not easy to fall off during use, and the life of the composite cathode is increased. After repeated use of the composite cathode 4 times, the decolorization rate of the target pollutant is still above 93%.
Description
Technical field
The present invention relates to the application of Persistent organic pollutants in process water and waste water, be specifically related to a kind of load iron ionic activity Carbon fibe composite cathode, preparation method and application thereof.
Background technology
Organism after conventional biological treatment in secondary effluent, the difficult biodegradable organism of a part, another part is biological own metabolism product and biological incomplete decomposing product own, and this part material has the constructional feature of humic acid material.
Wherein Persistent organic pollutants are one of main sources of water environment pollution, due to its great majority there is bio-toxicity and can not degrade by conventional biological treatment technique, and absorption method only achieves the phase transition of this pollutant, does not remove from environment.Representative triphenylmethane dye malachite green (MG), has high toxicity, the toxic side effect such as high residue and carcinogenic, teratogenesis, mutagenesis, and quantity discharged is large, is difficult to realize standard biologic degraded.
And the organism that humic acid (HA) is obtained by animal remains incomplete decomposing as a class, be not only and cause colourity, foreign odor taste, water distributing pipe to corrode and sedimentary reason material, also be the presoma of chlorine disinfection by-product trichloromethane, and trichloromethane confirm as carcinogenic substance.Therefore, reduce the content of HA in water, improvement water quality is a very urgent task.The existing minimizing technology to HA in water is based on coagulant sedimentation and membrane technique, but these two class methods only achieve the phase transition to pollutent, and does not remove from environment.
Therefore using MG and HA as target contaminant, explore have efficiently refractory organic and humic acid pollutants, less energy-consumption, fast simple treatment process, have great significance undoubtedly.
The advanced oxidation processes being representative with Fenton (Fenton) reaction produces the hydroxyl radical free radical (OH) of Strong oxdiative ability, it and organic reaction have very low selectivity, mineralising efficiency is high, thus becomes the strong technology of the even mineralising Persistent organic pollutants of degrading.But traditional Fenton process need by additional H
2o
2, metal catalyst produces OH, wherein H
2o
2transport and storage etc. can increase process expense and operational risk, and do not consume in treating processes due to metal catalyst, need after reaction to make it be precipitated as mud to be removed, make complex process by regulating pH or adding the methods such as precipitation agent, processing cost increases, and causes secondary pollution.
Electric Fenton (Electro-Fenton, EF) process electrochemistry combined with Fenton's reaction, because dissolved oxygen produces H at negative electrode continued reduction
2o
2reagent, eliminates additional H
2o
2the shortcoming brought, and high-efficiency low energy consumption and be easy to control, but this technology existing all needs added metal catalyzer.Such as Qu (Dyespigm., 2005,65:227-233) etc. make negative electrode with ACF, by additional Fe
2+carry out electro-Fenton reaction process azo dye wastewater, react 360min under the condition of pH3.0 after, TOC clearance reaches 70%.Wang (Desalination, 2010,253:129-134) etc. use ACF to make negative electrode, by additional Fe
2+carry out electro-Fenton reaction process printing and dyeing mill waste water from dyestuff, react 240min under the condition of pH3.0 after, COD clearance reaches 70%.Lei (Prot., 2010,88:431-438) etc. use ACF to make negative electrode, by additional Mn
2+carry out the red waste water of electro-Fenton reaction process alkalescence, under the condition of pH3.0, react 200min rear decoloring rate reach 100%.Martinez Huitle C A (J.Environ.Chem.Eng., 2014,2:875-880) etc. use gas diffusion composite cathode to make negative electrode, by additional Fe
2+carry out electro-Fenton reaction dye wastewater treatment, react 240min under the condition of pH3.0 after, COD clearance reaches 90%.In these electric Fenton method, added metal catalyzer still cannot avoid the generation of mud, causes secondary pollution, limits its application.Jia (Water Res., 1999,33:881-884) etc. makes negative electrode with ACF, and the ACF with iron plate makes anode, and sacrificial anode iron plate carries out electro-Fenton reaction dye wastewater treatment, and percent of decolourization reaches 90%, COD clearance and reaches 80%.Can control H in real time by sacrificial anode
2o
2with Fe
2+proportioning, but iron plate is oxidized to Fe
2+enter the generation still cannot avoiding mud in system, cause secondary pollution.Therefore, the generation of even stopping mud how is reduced significant.
Summary of the invention
For the defect existed in prior art or deficiency, the activated carbon fiber composite cathode of load iron ion is the object of the invention is to be applied to electro-fenton process, iron ion is carried in the activated carbon fiber of bigger serface, under solution aerobic condition, makes oxygen produce H in cathodic reduction
2o
2while, OH is produced with the catalyzer iron direct reaction of load, and this system to be applied in process water MG in HA and dyeing waste water, overcome existing electric Fenton technology to need to add metal ion catalyst in system, and the defect of the complex process that must cause the follow-up by products such as the mud produced in a large number are removed, secondary pollution.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of load iron ionic activity Carbon fibe composite cathode, this composite cathode comprises the activated carbon fiber that load has iron ion.
An application for load iron ionic activity Carbon fibe composite cathode, is applied to electro-fenton process process containing humic acid waste water or process triphenylmethane dyeing waste water by load iron ionic activity Carbon fibe composite cathode.
Preferably, described electro-fenton process process triphenylmethane dyeing waste water, its treatment process comprises:
Working electrode is load iron ionic activity Carbon fibe composite cathode, and supporting electrode is platinum filament, and reference electrode is saturated calomel electrode;
Triphenylmethane dyeing waste water contains 0.025 ~ 0.075molL
-1na
2sO
4, regulate triphenylmethane dyeing waste water pH value of solution=2.0 ~ 4.0, preaeration carried out to triphenylmethane dyeing waste water solution, under-0.6 ~-1.5V current potential, potentiostatic deposition is carried out to triphenylmethane dyeing waste water solution.
Preferably, described preaeration is with 1.0 ~ 3.5Lmin in dyeing waste water solution
-1flow pass into oxygen or air 10min.
Preferably, described electro-fenton process process is containing humic acid waste water, and its treatment process comprises:
Working electrode is the activated carbon fiber composite cathode of load iron ion, and supporting electrode is platinum filament, and reference electrode is saturated calomel electrode;
Regulate containing humic acid wastewater pH=3 ~ 7, after preaeration 10min being carried out containing humic acid waste water, under-0.5V ~-10V current potential, carry out potentiostatic deposition to containing humic acid waste water.
A preparation method for load iron ionic activity Carbon fibe composite cathode, described preparation method is subsurface adsorption method, and the preparation process of the method comprises: the activated carbon fiber after acidification is placed in FeSO
4soak in solution, the activated carbon fiber deionized water after soaking is washed till neutral and dries and obtain load iron ion and mn ion activated carbon fiber composite cathode.
Preferably, described FeSO
4the concentration of solution is 0.66 ~ 1.31molL
-1.
Preferably, described acidification comprises activated carbon fiber is immersed the H that mass concentration is 30% ~ 50%
2sO
4soak in solution, the activated carbon fiber deionized water after soaking is washed till neutral post-drying.
A preparation method for load iron ionic activity Carbon fibe composite cathode, described preparation method is the precipitator method, and the preparation process of the method comprises:
Step one, activated carbon fiber pre-treatment: activated carbon fiber being immersed mass concentration is boil in the HCl solution of 3 ~ 8%, immersing mass concentration is again boil in the NaOH solution of 3 ~ 8%, be placed in deionized water again to boil, the activated carbon fiber deionized water through above-mentioned process is washed till neutral post-drying;
Step 2, activated carbon fiber-loaded iron ion: 0.18molL will be immersed through the pretreated activated carbon fiber of step one
-1feSO
4in solution, toward FeSO at 70 DEG C
4dropwise 5molL is added in solution
-1naOH solution 20 ~ 80ml, after stirring reaction 5h, rinses till the deionized water clarification after rinsing the activated carbon fiber after process with deionized water, the activated carbon fiber after flushing is dried and obtained the activated carbon fiber composite cathode of load iron ion.
The load iron ionic activity Carbon fibe composite cathode of preparation is applied to electro-fenton process process containing humic acid waste water or process triphenylmethane dyeing waste water.
Compared with prior art, advantage of the present invention is as follows:
(1) compared with the electro-fenton process of added metal catalyzer, iron is carried on ACF, has stopped the generation of mud, without the need to follow-up mud-water separation, simplified treatment process, non-secondary pollution;
(2) electro-Fenton reaction of added metal catalyzer mainly occurs in the solution, and the iron be carried on ACF can at the surperficial H that generate with dissolved oxygen electroreduction of composite cathode
2o
2reaction, enhances the reaction on composite cathode surface, avoids H
2o
2decomposition in the solution, decreases H
2o
2unfavorable side reaction, make OH output high, improve reaction efficiency;
(3) the acidic-group generation subsurface adsorption effect on iron and ACF surface, in use difficult drop-off, adds the composite cathode life-span, and after reusing 4 times, MG percent of decolourization still reaches more than 93%;
(5) reaction 100min, MG decolorization rate of wastewater can reach nearly 100%, COD clearance and can reach 96%; Reaction 180min, HA clearance can reach nearly 90%.Degradation efficiency is high, removes thoroughly.
Accompanying drawing explanation
Fig. 1 is the full spectrogram of XPS of Fe/ACF in embodiment 1;
Fig. 2 is Fe2p power spectrum spectrogram in the XPS of Fe/ACF in embodiment 1;
Fig. 3 is C1s power spectrum spectrogram in the XPS of Fe/ACF in embodiment 1;
Fig. 4 is the full spectrogram of XPS of Fe/ACF in embodiment 2;
Fig. 5 is Fe2p power spectrum spectrogram in the XPS of Fe/ACF in embodiment 2;
Fig. 6 is the fluorescence intensity change figure of the umbelliferone in embodiment 3 with the reaction times;
Fig. 7 is the reaction unit schematic diagram that Fe/ACF composite cathode of the present invention is applied to dyeing waste water;
Fig. 8 schemes in MG solution absorbance in embodiment 4 and reaction times;
Fig. 9 schemes in MG solution C OD clearance in embodiment 4 and reaction times;
Figure 10 schemes in HA clearance in embodiment 5 and reaction times;
Figure 11 schemes in MG solution percent of decolourization in embodiment 6 and reaction times;
Figure 12 schemes in MG solution percent of decolourization in embodiment 7 and reaction times;
Figure 13 schemes in MG solution percent of decolourization in embodiment 8 and reaction times;
Figure 14 schemes in HA clearance in embodiment 9 and reaction times;
Figure 15 schemes in MG solution percent of decolourization in embodiment 10 and reaction times;
Figure 16 schemes in HA clearance in embodiment 11 and reaction times;
Figure 17 schemes in MG solution percent of decolourization in embodiment 12 and reaction times;
Figure 18 schemes in MG solution percent of decolourization in embodiment 13 and reaction times;
Figure 19 schemes in MG solution percent of decolourization in embodiment 14 and reaction times;
Figure 20 schemes in MG solution percent of decolourization in embodiment 15 and reaction times;
Embodiment
Triphenylmethane dyeing waste water of the present invention for triphenylmethane dye (as malachite green) be applied to dyeing a kind of waste water of producing, be class Persistent organic pollutants.
Of the present invention is the organism that a class is obtained by animal remains incomplete decomposing containing humic acid waste water, as the organism in secondary effluent after conventional biological treatment, the difficult biodegradable organism of a part, another part is biological own metabolism product and biological incomplete decomposing product own, this part material has the constructional feature of humic acid material, is referred to as containing humic acid waste water.
" ACF " of the present invention represents activated carbon fiber, and " Fe/ACF " represents the activated carbon fiber of load iron ion, and " COD " represents chemical oxygen demand (COD), and " MG " represents malachite green, and " HA " represents humic acid.
The present invention passes through at ACF area load iron ion composition composite cathode, the H that dissolved oxygen electroreduction produces
2o
2produced the OH of strong oxidizing property by the iron ion catalysis on ACF surface and to carry out in degradation water MG in HA and dyeing waste water, other spikes (as superoxide radical) with oxidation capacity produced in this process also play the synergy of degradation process.
When subsurface adsorption legal system is for Fe/ACF, due to ACF surface under acidic conditions acidic-group (-COOH) can with the effect of metal ion generation subsurface adsorption, therefore with H
2sO
4aCF surface is processed, increases the acidic-group quantity on its surface, promote that ACF is to Fe
2+absorption, reach the object of load.
The preparation of following embodiment Malachite Green simulated wastewater: take 0.0600g malachite green solid and 2.8400g Na
2sO
4solid, is settled to 400mL after dissolving.The simulated wastewater Malachite Green concentration configured is 150mgL
-1, Na
2sO
4concentration is 0.05molL
-1.
The most difficult degradation of malachite green wastewater Malachite Green due to reality, toxic side effect is maximum, therefore with the actual malachite green wastewater of the malachite green wastewater of preparation simulation, adds Na
2sO
4as ionogen, strengthen the electroconductibility of malachite green simulated wastewater.
The preparation of humic acid simulated wastewater in following embodiment: measuring 21.941mL concentration is 364.6mgL
-1humic acid storing solution, take 2.8400g Na
2sO
4dissolution of solid, is settled to 400mL after mixing.In the simulated wastewater configured, humic acid concentration is 20mgL
-1, Na
2sO
4concentration is 0.05molL
-1.
Because in the humic acid waste water of reality, humic acid belongs to macromole, difficult for biological degradation, therefore with the humic acid waste water of the humic acid waste water of preparation simulation reality, add Na
2sO
4as ionogen, strengthen the electroconductibility of humic acid simulated wastewater.
In order to the application of the Fe/ACF composite cathode of the present invention of explanation clearly, be specifically described below in conjunction with Figure of description and embodiment.
In following examples waste water sample, MG concentration adopts ultraviolet-visible spectrophotometer to measure, and determined wavelength is that the percent of decolourization of 617nm, MG is calculated as follows:
Wherein A
0for the absorbance of MG before reaction under same pH, A
tfor reacting the absorbance of t MG under same pH.
In waste water sample, HA concentration adopts ultraviolet-visible spectrophotometer to measure, and determined wavelength is that the clearance of 254nm, HA is calculated as follows:
Wherein A
0for reacting the absorbance of front HA, A
tfor the absorbance of t HA.
In waste water sample, MG solution C OD adopts potassium dichromate process to measure, and COD clearance is calculated as follows:
Wherein C
0for the COD value of the MG solution before reaction, C
tfor the COD value of reaction t MG solution.
Embodiment 1: subsurface adsorption legal system characterizes for Fe/ACF composite cathode and XPS
The acidifying of step one, ACF: by 0.5g ACF (specific surface area 1500m
2g
-1) immerse 100mL 40% (mass concentration) H
2sO
4in solution, in constant temperature oscillator at 30 DEG C with 30rmin
-1speed oscillation soak after 24h and take out, wash 2 ~ 3 times with deionized water, dry 1h at 100 DEG C;
Step 2, ACF load iron ion: the ACF through step one acidifying is placed in 0.66molL
-1feSO
4in solution, in constant temperature oscillator at 30 DEG C with 30rmin
-1speed oscillation soak after 24h and take out, be washed till neutrality with deionized water, dry 1h at 100 DEG C;
Fe/ACF step 2 obtained is fixed on polyfluortetraethylene pipe with holes, obtains Fe/ACF composite cathode.
X-photoelectron spectrum (XPS) analyser is adopted to carry out ultimate analysis to Fe/ACF surface.
The results are shown in Figure 1, Fig. 2, Fig. 3.Known by the full spectrogram of the XPS of Fe/ACF, Fe/ACF mainly comprises carbon, oxygen, iron three kinds of elements.Calibrate with the C1s peak (284.5eV) of carbon atom, can load Fe on known ACF by combination corresponding to 2p3/2 peak in the power spectrum spectrogram of Fe2p
3+.In C1s power spectrum spectrogram, the peak of what main peak 284.68eV place was corresponding is charcoal skeleton in ACF, the small peak in left side is the C1s peak of carbon atom in ACF surface functional group carboxyl, illustrates through H
2sO
4after acidifying, the functional group on ACF surface is mainly carboxyl.
Embodiment 2: the precipitator method prepare Fe/ACF composite cathode and XPS characterizes
The pre-treatment of step one, ACF: by 0.4g ACF (specific surface area 1500m
2g
-1), be cut into 7cm × 9cm sheet, immerse heated and boiled 1h in the hydrochloric acid of 5%, remove possible impurity and mineral ion, after deionized water drip washing; Immerse 5% sodium hydroxide in heated and boiled 1h, after in deionized water, boil 1h, hold over night, be washed till neutrality with deionized water, dry 24h at 100 DEG C;
Step 2, ACF load iron ion: be fixed on support by the ACF through step one acidifying, immersion concentration is 0.18molL
-1feSO
4in solution, at 70 DEG C, dropwise add 5molL
-1sodium hydroxide solution 50mL, and stir load-reaction 5 hours.After having reacted, soak carrier surface with deionized water rinsing, till deionized water clarification, dry 1h at 100 DEG C.
Fe/ACF step 2 obtained is fixed on polyfluortetraethylene pipe with holes, obtains Fe/ACF composite cathode.
X-photoelectron spectrum (XPS) analyser is adopted to carry out ultimate analysis to Fe/ACF surface.
The results are shown in Figure 4, Fig. 5.Known by the full spectrogram of the XPS of Fe/ACF, Fe/ACF mainly comprises carbon, oxygen, iron three kinds of elements.Fe2p power spectrum is amplified, obtains Fig. 5.In figure, Fe2p photoelectron spectrum is by Fe2p
3/2and Fe2p
1/2two power spectrums are formed, and lay respectively near 712eV and 726eV.To comparatively sensitive Fe2p
3/2peak is analyzed, due to Fe
2+and Fe
3+combination can lay respectively at 709.5eV and 711.2eV place, load Fe on known ACF
3+.
Embodiment 3: the seizure of hydroxyl radical free radical (OH) in reaction
In 200mL beaker, add 0.05molL
-1na
2sO
4and 10mmolL
-1tonka bean camphor solution, regulator solution pH value is 3.0, and current potential is-1.0V, and oxygen-supply quantity is 2.0Lmin
-1, Fe/ACF composite cathode embodiment 1 prepared respectively is as working electrode, and volution platinum filament is supporting electrode, and saturated calomel electrode is reference electrode, and three electrodes are put into above-mentioned solution; Front 30min samples in the solution every 5min, rear 30min samples in the solution every 10min, fluorescence spectrophotometer is adopted to be 332nm in excitation wavelength, emission wavelength is the fluorescence intensity of 460nm place working sample, generate stable because tonka bean camphor can react with OH and there is the umbelliferone of fluorescent characteristics, therefore the fluorescence intensity measuring umbelliferone can reflect the amount that system produces OH.
As can be seen from the result of Fig. 6, in Fe/ACF cathodic electrochromic compound Fenton-like system, create OH.In reaction system, the fluorescence intensity of umbelliferone reflects the concentration of hydroxyl radical free radical, and before 15min, the fluorescence intensity increasing in time of umbelliferone increases gradually; From 15min to 30min, slow decline, declines rapidly after 30min.Before its major cause is 30min, umbelliferone is more stable, and along with reaction is carried out, the hydroxyl radical free radical produced in system makes umbelliferone degrade, thus the fluorescence intensity of solution is declined.
Embodiment 4: Fe/ACF composite cathode embodiment 1 prepared is applied to process MG waste water
As accompanying drawing 7, Fe/ACF composite cathode embodiment 1 prepared, is connected in electrochemical workstation three-electrode system with platinum filament and makes working electrode, supporting electrode volution platinum filament and reference electrode saturated calomel electrode is connected to electrochemical workstation simultaneously;
Three electrode head is submerged into 400mL containing finite concentration MG and 0.05molL
-1na
2sO
4simulated wastewater in, use H
2sO
4regulate initial soln pH=3.0 with NaOH, be filled with 2.0Lmin continuously
-1o
2, after preaeration 10min, under-1.0V current potential (vs saturated calomel electrode), carry out potentiostatic deposition, energising duration 160min.
Experimental result is shown in Fig. 8, Fig. 9, and known MG decolorization rate of wastewater reaches nearly 100%, COD clearance and reaches 96%.
Embodiment 5: Fe/ACF composite cathode embodiment 2 prepared is applied to process containing HA waste water
As accompanying drawing 7, Fe/ACF composite cathode embodiment 2 prepared, is connected in electrochemical workstation three-electrode system with platinum filament and makes working electrode, supporting electrode volution platinum filament and reference electrode saturated calomel electrode is connected to electrochemical workstation simultaneously;
Three electrode head is submerged into 400mL containing TOC=20mgL
-1hA and 0.05molL
-1na
2sO
4simulated wastewater in, use H
2sO
4regulate initial soln pH=3.0 with NaOH, be filled with O continuously
2, after preaeration 10min, under-1.0V current potential (vs saturated calomel electrode), carry out potentiostatic deposition, energising duration 184min.
Experimental result is shown in Figure 10, and in known waste water, HA clearance reaches 88.9%.
Embodiment 6: when embodiment 1 prepares Fe/ACF composite cathode, sulfuric acid concentration is on the impact of composite cathode performance
Load FeSO
4concentration: 0.66molL
-1
Reaction target solution volume: 400mL
Reaction target solution concentration: MG 150mgL
-1
Na
2sO
4concentration: 0.05molL
-1
Solution initial pH value: 3.0
Oxygen-supply quantity: 3.5Lmin
-1
Electrolytic potential :-1.0V
Adopt respectively mass concentration be 30%, 40%, 50% sulfuric acid acidifying is carried out to ACF after the Fe/ACF composite cathode prepared carry out electro-Fenton reaction, measure the percent of decolourization of MG.
The results are shown in Figure 11, after reaction proceeds to 160min, the percent of decolourization of MG is respectively 94.0%, 99.8%, 99.7% when sulfuric acid massfraction is 40%, and the decolorizing effect of MG is best.The removal of MG is that the adsorption of ACF itself and Fenton reagent oxidation system carry out the common results of oxidation removal to MG.There are some researches show, hydrogen ion concentration is higher, H
2sO
4better to the acidic-group modified effect on ACF surface, the acidic-group formed on surface is more, thus at the more Fe of ACF surface adsorption
3+, be conducive to producing more OH.But a large amount of acidic-group can interconnect, the duct of blocking ACF, weakens the adsorption of ACF to MG, the percent of decolourization of MG is reduced.
Embodiment 7: FeSO when embodiment 1 prepares Fe/ACF composite cathode
4strength of solution is on the impact of composite cathode performance
Acidifying H
2sO
4concentration: 40%
Reaction target solution volume: 400mL
Reaction target solution concentration: MG 150mgL
-1
Na
2sO
4concentration: 0.05molL
-1
Solution initial pH value: 3.0
Oxygen-supply quantity: 3.5Lmin
-1
Electrolytic potential :-1.0V
Adopt 0mol/L, 0.66mol/L, 1.31mol/LFeSO respectively
4solution carries out load to the ACF after acidifying, and the composite cathode of above-mentioned preparation is applied to electro-Fenton reaction, measures the percent of decolourization of MG.
The results are shown in Figure 12, during reaction 160min, the percent of decolourization of MG is respectively 96.2%, 99.8%, 99.6%.Knownly work as Fe
2+concentration is 0.66molL
-1during L, MG decolorizing effect is best.Work as Fe
2+concentration is lower than 0.66molL
-1time, the percent of decolourization of MG is along with Fe
2+the increase of concentration and increasing, its reason is along with Fe in reaction system
2+the increase of concentration, Fe
2+adsorptive capacity increase thereupon, catalysis H
2o
2the OH that reaction produces also increases, thus the percent of decolourization of MG is increased.But work as Fe
2+concentration is greater than 0.66molL
-1after, along with Fe
2+the increase of concentration, produces a large amount of OH, Fe in solution
2+fe is oxidized to by OH
3+, cathode surface avtive spot is occupied thus percent of decolourization decline.
Embodiment 8: in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 1, pH value of solution is on the impact of process MG waste water effect
Acidifying H
2sO
4concentration: 40%
Load FeSO
4concentration: 0.66molL
-1
Reaction target solution volume: 400mL
Reaction target solution concentration: MG 150mgL
-1
Na
2sO
4concentration: 0.05molL
-1
Oxygen-supply quantity: 3.5Lmin
-1
Electrolytic potential :-1.0V
Regulate MG wastewater pH to be 2.0,3.0,4.0, measure the percent of decolourization of MG.
The results are shown in Figure 13, can principal reaction 160min time, the percent of decolourization of MG is respectively 96.3%, 99.8%, 99.7%.When simulated wastewater initial pH value is 3.0, decolorizing effect is best.When reacting initial pH and being lower, H in solution
+concentration increases, and not only can suppress Fe
3+be reduced into Fe
2+, and can promote that H+ is converted into H
2, make generation H
2o
2reactive site reduce, reaction generate OH reduce, percent of decolourization decline.The pH value initial along with solution increases, and in solution, OH-concentration increases, and is suppressing the generation of OH, thus percent of decolourization is reduced.
Embodiment 9: in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 2, pH value of solution is on the impact of process HA waste water effect
Reaction target solution volume: 400mL
Reaction target solution concentration: HA 20mg.L
-1
Na
2sO
4concentration: 0.05molL
-1
Electrolytic potential :-1.0V
Regulate HA pH value of solution to be 3.0,5.0,7.0, measure the clearance of HA.
The results are shown in Figure 14, can principal reaction 160min time, the clearance of HA is respectively 88.9%, 18.6%, 22.4%.When simulated wastewater initial pH value is 3.0, removal effect is best.The pH value initial along with solution increases, and in solution, OH-concentration increases, and is suppressing the generation of OH, thus clearance is reduced.
Embodiment 10: in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 1, different electrolytic potential is on the impact of process MG waste water effect
Acidifying H
2sO
4concentration: 40%
Load FeSO
4concentration: 0.66molL
-1
Reaction target solution volume: 400mL
Reaction target solution concentration: MG 150mgL
-1
Na
2sO
4concentration: 0.05molL
-1
Solution initial pH value: 3.0
Oxygen-supply quantity: 3.5Lmin
-1
When electrolytic potential is set to-0.6V ,-1.0V ,-1.5V respectively, measure the percent of decolourization of MG.
The results are shown in Figure 15, during reaction 160min, the percent of decolourization of MG is respectively 96.8%, 99.8%, 94.3%.Can find out, electrolytic potential increases from-0.6 to-1.0V percent of decolourization along with negative the moving of current potential, along with the negative of electrolytic potential moves, and Fe
3+more easily be reduced to Fe
2+, and Fe
2+again can with electroluminescent H
2o
2reaction generates Fe
3+and OH, speed of reaction is increased.But when current potential is negative move to-1.5V time, percent of decolourization declines on the contrary.This may be because the too negative meeting of current potential causes H
2o
2decomposition, make its density loss, thus make H in system
2o
2concentration reduce, have direct impact to oxidation capacity, make whole reaction process relatively slow.
Embodiment 11: in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 2, different electrolytic potential is on the impact of process HA solution efficacy
Reaction target solution volume: 400mL
Reaction target solution concentration: HA 20mg.L
-1
Na
2sO
4concentration: 0.05molL
-1
Solution initial pH value: 3.0
When electrolytic potential is set to-0.5V ,-1.0V ,-2.0V ,-4.0V ,-6.0V ,-8.0V ,-10.0V respectively, measure the clearance of HA.
The results are shown in Figure 16, during reaction 160min, the clearance of HA is respectively 84.7%, 88.9%, 74%, 67.5%, 60.6%, 56.2%, 65.8%.Can find out, when electrolytic potential is-1.0V, HA removal effect is best.
Embodiment 12: in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 1, different oxygen-supply quantity is on the impact of process MG waste water effect
Acidifying H
2sO
4concentration: 40%
Load FeSO
4concentration: 0.66molL
-1
Reaction target solution volume: 400mL
Reaction target solution concentration: malachite green 150mgL
-1
Na
2sO
4concentration: 0.05molL
-1
Solution initial pH value: 3.0
Electrolytic potential :-1.0V
Respectively with 1.0Lmin
-1, 2.0Lmin
-1, 3.5Lmin
-1flow in reaction soln, pass into pure oxygen, measure the percent of decolourization of MG.
The results are shown in Figure 17, during reaction 23min, the percent of decolourization of MG is respectively 52.3%, and 94.0%, 87.7%.Oxygen-supply quantity is 2.0Lmin
-1time MG decolorizing effect best.
Embodiment 13: different N a in Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 1
2sO
4concentration is on the impact of process MG waste water effect
Acidifying H
2sO
4concentration: 40%
Load FeSO
4concentration: 0.66molL
-1
Reaction target solution volume: 400mL
Reaction target solution concentration: MG 150mgL
-1
Solution initial pH value: 3.0
Oxygen-supply quantity: 2.0Lmin
-1
Electrolytic potential :-1.0V
Na in malachite green wastewater
2sO
4concentration is respectively 0.025molL
-1, 0.05molL
-1, 0.075molL
-1, measure the percent of decolourization of MG.
The results are shown in Figure 18, during reaction 23min, MG percent of decolourization is respectively 34.7%, and 94.0%, 41.1%.Work as Na
2sO
4concentration is from 0.025molL
-1be increased to 0.05molL
-1time, percent of decolourization is along with Na
2sO
4the increase of concentration and increasing, works as Na
2sO
4concentration reaches 0.05molL
-1time decolorizing effect best, afterwards along with the increase percent of decolourization of concentration reduces gradually.
Embodiment 14: Fe/ACF composite cathode electro-Fenton reaction prepared by embodiment 1 and ACF adsorption experiment contrast the decolorizing effect of MG waste water
By 0.5g ACF (specific surface area 1500m
2g
-1) be fixed on polyfluortetraethylene pipe with holes, be placed in 400mL (150mgL
-1) in MG solution, standing adsorption 180min, certain hour interval its absorbancy of sampling and measuring, obtains the percent of decolourization of ACF adsorption experiment process MG waste water, is contrasted by the MG percent of decolourization of the Fe/ACF composite cathode electro-Fenton reaction of itself and embodiment 1.
The results are shown in Figure 19, the removal of known ACF adsorption experiment MG is starkly lower than the electro-Fenton reaction of Fe/ACF composite cathode to the percent of decolourization of MG waste water, illustrates that Fe/ACF composite cathode electro-Fenton reaction efficiency is high.
Process MG waste water reused by embodiment 15:Fe/ACF composite cathode
To the electro-Fenton reaction of embodiment 4, certain hour interval samples, and reacts and stops to during 92min, by Fe/ACF deionized water drip washing 2 times, is placed in dry 20min at 100 DEG C, baking oven.Use the same method and carry out subsequent reactions, respectively at 92min, 180min, 300min stopped reaction, reuse 4 times altogether.
The results are shown in Figure 20, after known Fe/ACF composite cathode reuses 4 times, MG percent of decolourization still can reach more than 93%, this shows, the Fe/ACF composite cathode life-span is long, reusable.
Claims (10)
1. a load iron ionic activity Carbon fibe composite cathode, is characterized in that, this composite cathode comprises the activated carbon fiber that load has iron ion.
2. an application for load iron ionic activity Carbon fibe composite cathode, is characterized in that, load iron ionic activity Carbon fibe composite cathode is applied to electro-fenton process process containing humic acid waste water or process triphenylmethane dyeing waste water.
3. the application of the activated carbon fiber composite cathode of load iron ion as claimed in claim 2, it is characterized in that, described electro-fenton process process triphenylmethane dyeing waste water, its treatment process comprises:
Working electrode is load iron ionic activity Carbon fibe composite cathode, and supporting electrode is platinum filament, and reference electrode is saturated calomel electrode;
Triphenylmethane dyeing waste water contains 0.025 ~ 0.075molL
-1na
2sO
4, regulate triphenylmethane dyeing waste water pH value of solution=2.0 ~ 4.0, preaeration carried out to triphenylmethane dyeing waste water solution, under-0.6 ~-1.5V current potential, potentiostatic deposition is carried out to triphenylmethane dyeing waste water solution.
4. the application of the activated carbon fiber composite cathode of load iron ion as claimed in claim 3, it is characterized in that, described preaeration is with 1.0 ~ 3.5Lmin in dyeing waste water solution
-1flow pass into oxygen or air 10min.
5. the application of the activated carbon fiber composite cathode of load iron ion as claimed in claim 2, is characterized in that, described electro-fenton process process is containing humic acid waste water, and its treatment process comprises:
Working electrode is the activated carbon fiber composite cathode of load iron ion, and supporting electrode is platinum filament, and reference electrode is saturated calomel electrode;
Regulate containing humic acid wastewater pH=3 ~ 7, after preaeration 10min being carried out containing humic acid waste water, under-0.5V ~-10V current potential, carry out potentiostatic deposition to containing humic acid waste water.
6. a preparation method for load iron ionic activity Carbon fibe composite cathode, is characterized in that, described preparation method is subsurface adsorption method, and the preparation process of the method comprises: the activated carbon fiber after acidification is placed in FeSO
4soak in solution, the activated carbon fiber deionized water after soaking is washed till neutral and dries and obtain load iron ion and mn ion activated carbon fiber composite cathode.
7. the preparation method of load iron ionic activity Carbon fibe composite cathode as claimed in claim 6, is characterized in that, described FeSO
4the concentration of solution is 0.66 ~ 1.31molL
-1.
8. the preparation method of load iron ionic activity Carbon fibe composite cathode as claimed in claims 6 or 7, is characterized in that, described acidification comprises activated carbon fiber is immersed the H that mass concentration is 30% ~ 50%
2sO
4soak in solution, the activated carbon fiber deionized water after soaking is washed till neutral post-drying.
9. a preparation method for load iron ionic activity Carbon fibe composite cathode, is characterized in that, described preparation method is the precipitator method, and the preparation process of the method comprises:
Step one, activated carbon fiber pre-treatment: activated carbon fiber being immersed mass concentration is boil in the HCl solution of 3 ~ 8%, immersing mass concentration is again boil in the NaOH solution of 3 ~ 8%, be placed in deionized water again to boil, the activated carbon fiber deionized water through above-mentioned process is washed till neutral post-drying;
Step 2, activated carbon fiber-loaded iron ion: 0.18molL will be immersed through the pretreated activated carbon fiber of step one
-1feSO
4in solution, toward FeSO at 70 DEG C
4dropwise 5molL is added in solution
-1naOH solution 20 ~ 80ml, after stirring reaction 5h, rinses till the deionized water clarification after rinsing the activated carbon fiber after process with deionized water, the activated carbon fiber after flushing is dried and obtained the activated carbon fiber composite cathode of load iron ion.
10. load iron ionic activity Carbon fibe composite cathode prepared by claim 6,7,8 or 9 is applied to electro-fenton process process containing humic acid waste water or process triphenylmethane dyeing waste water.
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| CN105036259A (en) * | 2015-07-01 | 2015-11-11 | 湖南大学 | Modification method of double-metal-modified activated carbon fiber electrode by electrolytic deposition and application |
| CN106139933A (en) * | 2016-06-24 | 2016-11-23 | 辽宁科技学院 | A kind of preparation method of reactive electrochemical cathode film |
| CN106423276A (en) * | 2016-09-13 | 2017-02-22 | 合肥工业大学 | Preparation method of nickel electric Fenton catalyst supported by nitrogen mixed with carbon |
| CN107601624A (en) * | 2017-10-26 | 2018-01-19 | 清华大学 | A kind of preparation and application of the electric Fenton cathode material based on carried-type active Carbon fibe |
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