CN117923598B - Method for degrading phenolic pollutants in industrial wastewater by using photoelectric Fenton - Google Patents
Method for degrading phenolic pollutants in industrial wastewater by using photoelectric Fenton Download PDFInfo
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Classifications
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- 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
-
- 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
- C02F2001/46152—Electrodes characterised by the shape or form
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for degrading phenolic pollutants in industrial wastewater by using photoelectric Fenton, which combines a photoelectric catalytic oxidation technology and a Fenton-like oxidation technology into a novel photoelectric Fenton technology, and improves the generating capacity of an oxidant OH and the pollutant degradation capacity under visible light irradiation in a synergistic way, so that the phenolic wastewater treatment cost is reduced. The photoelectric Fenton wastewater treatment system is composed of a photoelectric Fenton groove, an H 2O2 metering groove, an alkali solution metering groove and a xenon lamp light source, a photo anode in the photoelectric Fenton groove is irradiated by visible light, the photo anode is connected with a foam copper cathode by a wire, and photoelectrons generated by photo anode Ag/TiO 2/BiFeO3 are transmitted to the foam copper cathode by an internal electric field of the photo anode; and the OH generated by photoelectrocatalysis on the photoanode and the foamy copper cathode and the OH generated by the Fenton reaction of the externally added H 2O2 type degrade phenolic pollutants in the wastewater together. The photoelectric Fenton technology does not need an external electric field, has simple phenolic wastewater treatment equipment and large wastewater treatment capacity, and has industrial application prospect.
Description
Technical Field
The invention relates to a method for degrading phenolic pollutants in industrial wastewater by using photoelectric Fenton, and belongs to the technical fields of new materials and environmental protection water treatment.
Background
Economical and efficient treatment of phenolic wastewater is a challenging problem, and professionals expect advanced oxidation technologies such as photocatalysis technology, photoelectrocatalysis technology, photoFenton technology and photoelectroFenton technology to play an important role in phenolic wastewater treatment, and have conducted a great deal of research work.
The photocatalysis method is to utilize a photocatalyst to absorb light energy to generate photo-generated electron and hole pairs, and the photo-generated electron and hole pairs react with water and oxygen in the environment to form hydroxyl free radicals OH and superoxide ions O 2 - with strong oxidability, so that organic pollutants are further oxidized and degraded into CO 2 and H 2 O. In theory, organic pollutants adsorbed on the surface of the photocatalyst can be degraded only by using sunlight to irradiate the photocatalyst, the wastewater treatment cost is almost zero, but the photo-generated electrons and holes are very easy to be compounded, the photocatalysis efficiency is very low, and the practical application requirement cannot be met. The technical key is the design and preparation of the high-efficiency photocatalyst so as to inhibit the recombination of photo-generated electrons and holes and improve the photocatalysis efficiency.
Photoelectrocatalysis is a high-grade oxidation technique combining electrocatalytic and photocatalytic methods. The traditional photoelectrocatalysis method mainly comprises electrolytic oxidation, so that the power consumption is high, and the technical economy is not realized; professionals consider that only low voltage is applied or an endogenous electric field is utilized to effectively separate photo-generated electrons and holes generated by a photo-catalytic method so as to improve photo-catalytic efficiency, and the problems of low-OH generation capacity and low generation efficiency cannot be solved, so that the photo-catalytic method is difficult to be practically applied.
Fenton or Fenton-like methods are advanced oxidation techniques that use Fe 2+ or other substances to catalyze the reduction of H 2O2 to produce OH, which further oxidizes and degrades organic contaminants into CO 2 and H 2 O. The Fenton method is industrially applied to wastewater treatment under a plurality of conditions because the mass of H 2O2 produced by reduction is large enough and the speed is high enough. The heterogeneous catalyst is used for replacing the homogeneous catalyst, so that the defects of high catalyst consumption, high treatment cost and the like of the Fenton-like method are gradually overcome, and the method has wide application prospect.
Electro-Fenton method is a high-grade oxidation technique that employs an electrolytic process to produce at least one feedstock of Fenton method in situ. Comprises that only electrolytic oxidation is carried out to produce Fe 2+; only electrolytic reduction to produce Fe 2+ or Fe 0; only electrolytic reduction to produce H 2O2; at the same time, the electrolytic oxidation produces Fe 2+ and the electrolytic reduction produces H 2O2. The wastewater treatment cost can be reduced by 40% at most, the secondary pollution of iron mud can be reduced, and a plurality of cases of successful industrialization application exist, but the defect of relatively low capacity of the electro-Fenton method H 2O2 can not be overcome, and the application and popularization of the electro-Fenton method are affected.
The photo Fenton method is a Fenton method or Fenton-like method under light irradiation, and is sometimes classified into Fenton-like methods, and light energy is considered as a Fenton-like catalyst. The light energy input can reduce the consumption of the H 2O2 oxidant and the Fenton-like catalyst, reduce the wastewater treatment cost, and the prior successful case of pilot-scale wastewater treatment by the ultraviolet Fenton method has great application value, and the technical development is widely emphasized.
The electro-optic Fenton method can be an electro-assisted photo-Fenton method or a photo-assisted electro-Fenton method, which is essentially a combination of electro-optic catalysis and Fenton-like methods. Based on the generation of OH by the photoelectrocatalysis method, more OH is cooperatively generated by the Fenton-like method, so that the technical problems of low capability of degrading organic pollutants and low treatment efficiency of the photoelectrocatalysis method are solved, and the method is an important development direction of efficient utilization of solar energy. The photoelectric Fenton method is an internal electric field assisted Fenton-like method, and because the photoelectric catalytic oxidation is carried out in a non-biased state, not only is the separation of photo-generated electrons and holes enhanced by utilizing the internal electric field of a photo-anode, but also the oxidation of H 2O2 in a photoelectric Fenton groove is prevented, and the simplification of a wastewater treatment process and equipment is realized.
Early patent CN100509639C discloses a method for treating refractory organic wastewater by photoelectrocatalysis of an inclined-plate type liquid film, wherein a TiO 2 photocatalyst is fixed on a stainless steel or titanium substrate by a direct thermal oxidation method or a sol-gel method to be used as a photo-anode, the photo-anode is placed in a reaction tank at an inclined angle of 60 DEG, the upper part of the photo-anode is connected with a liquid storage tank, and the bottom is immersed in the wastewater; the Cu sheet is used as a cathode, the photo-anode and the Cu cathode are respectively connected with the anode and the cathode of a direct current power supply, the voltage is regulated to be 0.6-1.0V, the peristaltic pump is used for pumping the wastewater from the reaction tank into the liquid storage tank, the wastewater overflows through the liquid storage tank and flows over the surface of the photo-anode to form a layer of liquid film, and the surface of the photo-anode can be irradiated only through the liquid film by exciting light. The invention greatly reduces the absorption of organic wastewater to light, improves the utilization rate of an excitation light source and the photoelectrocatalysis degradation efficiency, and simultaneously the circulating flow of the wastewater quickens the exchange and update of the electrode surface and main solution substances, strengthens the mass transfer and improves the degradation efficiency. The TiO 2 photo-anode can generate photoelectric effect only by ultraviolet irradiation, and an external electric field complicates water treatment equipment and cannot achieve expected technical economy, but the invention has great reference value.
Patent CN113603181B discloses a method for degrading oxytetracycline by double-chamber photoelectrocatalysis, which comprises the steps of constructing a double-chamber photoelectrocatalysis system and degrading oxytetracycline by the photoelectrocatalysis system under the irradiation of a xenon lamp, wherein a graphite-phase carbon nitride doped titanium dioxide nanotube array photoelectrode is prepared by a one-step method, so that the oxytetracycline is efficiently degraded. The double-chamber photoelectrocatalysis equipment is complex, has great technical amplification and practical application difficulty, and is only limited to laboratory research.
Patent CN109824120a discloses a graphite-phase carbon nitride modified antimony-doped tin dioxide composite photoelectrocatalysis electrode, a preparation method and application, wherein graphite-phase carbon nitride is added in preparation of tin-antimony sol gel, and a sol-gel coating thermal decomposition method is adopted to prepare the composite photoelectrocatalysis electrode. The photoelectric performance experiment shows that the composite photoelectric catalytic electrode has higher catalytic activity and visible light absorption compared with an antimony-doped tin dioxide electrode, and has potential application prospect in the fields of solar energy utilization and wastewater treatment. The problems of low OH concentration, low yield efficiency and extremely low wastewater treatment capacity are also limited to laboratory researches, and the expansion and practical application are difficult.
Meanwhile, the perovskite material bismuth ferrite BiFeO 3 with ferroelectricity and ferromagnetism has relatively narrow forbidden bandwidth and strong visible light absorption capacity, so that the perovskite material bismuth ferrite BiFeO 3 can show excellent photovoltaic characteristics under the irradiation of visible light. Bismuth ferrite is used as a photocatalyst for photocatalytic degradation of organic pollutants for the first time in 2006. The research shows that the modification of BiFeO 3 by nano Ag, nano TiO 2 or graphite phase carbon nitride g-C 3N4 can improve the photocatalytic performance and the capability of degrading organic pollutants.
Patent CN104671671B discloses a nano silver/bismuth ferrite composite film and a preparation method thereof, wherein uniformly dispersed nano silver particles are introduced into a bismuth ferrite film matrix through a sol-gel method and heat treatment, so that the nano silver/bismuth ferrite composite film is formed. The composite film has typical magnetism, and the dielectric constant is improved by 2-4 times.
The nano TiO 2 is used as a template and an adhesive, silver with good conductivity and bismuth ferrite with ferroelectricity are loaded on the nano TiO 2, and the prepared nano Ag/TiO 2/BiFeO3 composite Fenton-like catalyst has better performance of catalyzing H 2O2 to generate OH and has the capability of degrading phenolic pollutants in industrial wastewater; when the cathode is used as a photo-anode, the separation efficiency of photo-generated electrons and holes is higher due to the action of an endogenous electric field, and the cathode has better photoelectrocatalysis performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for degrading phenolic pollutants in industrial wastewater by using photo-Fenton, which is efficient and low in cost, so as to meet the requirements of industrial application.
The preparation method of the photo-anode coating hydrosol comprises the following specific steps:
S1: dissolving butyl titanate in absolute ethyl alcohol to form butyl titanate ethanol solution, dripping the butyl titanate ethanol solution into nitric acid ethanol water solution, and hydrolyzing to form acidic nano TiO 2 ethanol hydrosol, wherein the molar ratio of butyl titanate to ethanol to nitric acid is 1:10-30:0.1-0.5;
S2: bismuth nitrate and ferric nitrate are dissolved in a citric acid aqueous solution to obtain nano bismuth ferrite precursor hydrosol, wherein the molar ratio of the bismuth nitrate to the ferric nitrate to the citric acid is 1:1:2-4;
S3: mixing nano bismuth ferrite precursor hydrosol with acidic nano TiO 2 ethanol hydrosol, adding silver nitrate aqueous solution, and aging for 12-24 hours to form photo-anode coating aqueous sol, wherein the molar ratio of bismuth nitrate, ferric nitrate, butyl titanate and silver nitrate is 1:1:3-4:0.2-0.4.
The preparation method of the Ag/TiO 2/BiFeO3 photo-anode comprises the following specific steps:
(1) Cutting and processing a titanium plate collector into a concave inclined plate shape capable of condensing light, polishing and brightening by sand paper, soaking and coarsening by using a mixed aqueous solution of nitric acid and ammonium fluoride, washing and drying to obtain a photo-anode collector;
(2) Coating photo-anode coating hydrosol on a titanium plate collector, and repeating the coating for 3-5 times after gel drying and curing until the thickness of a surface wet film is 5-10 mu m;
(3) Placing the solidified film-coated titanium plate collector electrode into a high-temperature furnace, heating to 500-700 ℃, and carrying out heat preservation and sintering for 1-4h to form an Ag/TiO 2/BiFeO3 photo-anode, wherein the thickness of the surface film is 3-5 mu m, and the mass composition of the surface film is as follows: 3-6% of Ag and 45-60% of TiO 235%-50%,BiFeO3.
The construction method of the photoelectric Fenton wastewater treatment system comprises the following specific steps of:
Step one: the photoelectric Fenton reaction tank, the H 2O2 metering tank, the alkali solution metering tank and the xenon lamp light source are assembled to construct a photoelectric Fenton wastewater treatment system, and the core part is the photoelectric Fenton reaction tank;
Step two: a concave inclined plate-shaped photo-anode capable of condensing light is fixed in the photoelectric Fenton groove at an angle of 45 ◦-70◦ degrees;
Step three: and fixing a foam copper cathode with the same concave inclined plate shape, and communicating the photo anode with the foam copper cathode through a switch and a lead.
The specific steps of degrading phenolic pollutants in industrial wastewater in the invention are as follows:
t1: injecting 0.05-0.5g/L phenolic wastewater into the photoelectric Fenton tank, and immersing a photoanode and a foamy copper cathode with the heights of about 1/5-1/3;
T2: circularly spraying phenolic wastewater in the photoelectric Fenton groove to the upper end of the photo-anode by using a peristaltic pump, forming a liquid film of 10-100 mu on the surface of the photo-anode, and irradiating the photo-anode by using visible light emitted by a xenon lamp;
T3: circularly spraying phenolic wastewater in the photoelectric Fenton tank to the upper end of the foam copper cathode by using a peristaltic pump, and forming a liquid film with the flow velocity of 1-3m/s on the surface of the foam copper cathode;
T4: adding sodium hydroxide aqueous solution to maintain the pH=3-7 of the phenolic wastewater in the photoelectric Fenton tank;
T5: adding H 2O2 aqueous solution into the phenolic wastewater to ensure that the initial concentration of H 2O2 in the phenolic wastewater is 0.05-1.0g/L;
T6: and (5) periodically sampling and measuring the concentration of the phenolic pollutants in the phenolic wastewater, and calculating the change rate of the concentration of the phenolic pollutants in the phenolic wastewater.
Experiments show that the binary composite material Ag/BiFeO 3、TiO2/BiFeO3、Ag/TiO2、BiFeO3/TiO2 has better visible light catalytic performance than single-component photocatalytic material, and the composite or doping of the two materials expands the light absorption range and improves the photocatalytic efficiency.
The ternary composite material Ag/TiO 2/BiFeO3 has excellent visible light catalytic performance, and silver doping not only increases the conductivity of the composite material, but also ensures that the photocatalytic performance of the ternary composite material Ag/TiO 2/BiFeO3 hardly changes along with the increase of the upper film thickness of the photo-anode. The ternary material composite is equivalent to a ladder in the quantized energy level, so that a refined energy level structure is increased, the photoresponse range is enlarged, the specific surface area of the material is enlarged, and the photocatalysis efficiency is improved. Even in the absence of light, the heterogeneous Fenton-like catalyst is good and can catalyze and decompose H 2O2 to generate OH.
The photoelectric Fenton wastewater treatment system consists of a photoelectric Fenton reaction tank, an H 2O2 metering tank, a sodium hydroxide solution metering tank and a xenon lamp light source, wherein the photoelectric Fenton reaction tank is used as a core part, and a process flow block diagram is shown in an attached figure 1 of the specification.
In the invention, phenolic wastewater is sprayed to the upper end of a concave inclined plate photoanode by a peristaltic pump, and is circulated into a photoelectric Fenton wastewater tank, a liquid film is formed on the surface of the photoanode by the phenolic wastewater, and visible light irradiates the surface of the photoanode through the liquid film to perform a photoelectric catalytic reaction, so that phenolic pollutants in the wastewater are oxidized and degraded; the H 2O2 metering tank provides an aqueous solution of the H 2O2 oxidant, so that Fenton-like oxidation reaction is rapidly carried out; the sodium hydroxide solution metering tank provides sodium hydroxide aqueous solution, and organic acid generated by oxidation is neutralized to control pH=3-7 range required by Fenton reaction of phenolic wastewater; meanwhile, phenolic wastewater is sprayed to the upper end of a concave foamy copper cathode by another peristaltic pump, and is circulated to a photoelectric Fenton wastewater tank, a liquid film with a relatively fast flow speed is formed on the surface of the foamy copper cathode, photo-generated electrons on a photo-anode are transferred to the foamy copper cathode, and the photo-generated electrons can electrically reduce dissolved O 2 in the phenolic wastewater into H 2O2 through the following reaction O 2+2H++2e→H2O2, so that organic pollutants in the OH oxidation wastewater are further generated; h 2O2 in the wastewater can also be electrically reduced to generate OH through the following reaction H 2O2+e→·OH+ OH-, and organic pollutants in the wastewater can be further oxidized.
The core of the photoelectric Fenton wastewater treatment system is a photoelectric Fenton reaction tank, and the composition schematic diagram of the photoelectric Fenton wastewater treatment system is shown in the attached figure 2 of the specification.
A light anode in a concave inclined plate shape capable of focusing is fixed in the photoelectric Fenton groove at an angle of 45 ◦-70◦ degrees, and then a foam copper cathode in the same concave inclined plate shape is fixed; the photo anode is communicated with the foam copper cathode through a switch and a wire; injecting phenolic wastewater to be treated into the photoelectric Fenton tank, and immersing a photoanode and a foamy copper cathode with the heights of about 1/5-1/3; circularly spraying phenolic wastewater in the photoelectric Fenton groove to the upper end of the photo-anode by using a peristaltic pump, and irradiating a liquid film formed on the photo-anode by using visible light emitted by a xenon lamp; and (3) circularly spraying phenolic wastewater in the photoelectric Fenton tank to the upper end of the foam copper cathode by using a peristaltic pump, and forming a liquid film with the flow velocity of 1-3m/s on the foam copper cathode.
In the invention, bisphenol A and p-hydroxy benzene hydantoin which are phenolic pollutants in industrial wastewater are taken as typical phenolic pollutant targets for photoelectric Fenton degradation research objects. Bisphenol A is a chemical raw material for producing resin and paint, the products are widely applied in daily life, the hazard of bisphenol A in industrial wastewater is relatively large, and an economic and efficient treatment method needs to be developed; the p-hydroxy phenylhydantoin is a raw material of amoxicillin, has relatively large industrial production, is difficult to treat phenolic pollutants, and needs to be researched and developed to prepare a new treatment method.
The invention carries out comparison research on the conditions of Fenton-like oxidation under no illumination, photoelectrocatalytic oxidation under visible light illumination, photoFenton oxidation under visible light illumination and photoFenton oxidation under visible light illumination, and the degradation effect is compared by measuring the change of the concentration of the phenolic pollutants in the photoFenton tank with time under different oxidation modes and comparing the change rate of the concentration of the phenolic pollutants. Experiments show that the combination of photoelectrocatalytic oxidation and Fenton-like oxidation produces synergistic oxidation, and the change rate of the concentration of pollutants in wastewater is obviously increased. The main reason is that the combination of the photoelectrocatalysis oxidation and Fenton-like oxidation forms a new technology of photoelectroFenton oxidation, under the irradiation of visible light, the concentration of OH generated by the cooperation of the photoelectrocatalysis oxidation and Fenton-like oxidation is relatively high, the concentration of OH is relatively stable, and the oxidation capability of OH is enhanced.
The effect of degrading phenolic pollutants is compared by the binary TiO 2/BiFeO3 photocatalytic material and the ternary Ag/TiO 2/BiFeO3 photocatalytic material, so that the important effect of silver doping on improving the separation and transmission efficiency of photo-generated electrons is further proved.
Compared with the prior art, the invention has outstanding substantive features and obvious technical progress in the following aspects: (1) The ternary composite material Ag/TiO 2/BiFeO3 has good conductivity, inhibits the recombination of photo-generated electrons and holes, and improves the electron transmission efficiency and the photocatalysis efficiency;
(2) The concave inclined plate-shaped photo-anode is adopted for condensation, only less than 1/3 of the photo-anode is immersed in the phenolic wastewater, the light-receiving area of a liquid film on the surface of the photo-anode is large, and the photoelectrocatalysis efficiency is improved;
(3) The photo-anode film material and the foam copper cathode material are Fenton-like catalysts, can be used for heterogeneous catalytic decomposition of H 2O2 to generate a large amount of OH, and can be used for synergetically oxidizing and degrading phenolic pollutants in the wastewater;
(4) The foam copper cathode effectively utilizes electrons generated by the photo anode to reduce dissolved oxygen in wastewater into H 2O2 or H 2O2 in the wastewater to generate OH by electro-Fenton reaction, and no external electric energy is needed;
(5) The photoelectric Fenton tank adopts a single-chamber structure, the wastewater treatment equipment is simple, the process conditions are easy to control, and the industrial application is easy;
(6) Under the irradiation of visible light, the OH generated by the photo-electro-catalysis and Fenton-like reaction synergistically degrades phenolic pollutants in the wastewater, so that the oxidizing capability of the phenolic pollutants in the wastewater is improved, and the consumption of externally added H 2O2 is reduced.
The invention has the advantages and positive effects that:
(1) Under the irradiation of visible light, the invention has the industrial application prospect that OH generated by the photoelectrocatalysis and Fenton-like reaction synergistically degrades phenolic pollutants in the wastewater;
(2) The photo-anode Ag/TiO 2/BiFeO3 can inhibit the recombination of photo-generated electrons and holes, generate more OH and can efficiently degrade phenolic pollutants in wastewater;
(3) The internal electric field of the photo-anode material enables photo-generated electrons on the photo-anode to be transferred to the foam copper cathode, the electro-Fenton reaction occurs, dissolved oxygen is reduced to generate H 2O2, and the photo-catalytic efficiency is improved.
The raw materials of butyl titanate, bismuth nitrate, ferric nitrate, silver nitrate, nitric acid, ammonium fluoride, phenolic products, absolute ethyl alcohol, amoxicillin, titanium plates and copper plates adopted by the invention are all commercial chemical reagents.
Drawings
FIG. 1 is a process flow diagram of the photoelectric Fenton wastewater treatment system of the invention.
FIG. 2 is a schematic diagram of a photo Fenton reaction cell according to the present invention;
In the figure, 1-photo anode. 2-foamy copper cathode, 3-xenon lamp source, 4-photoelectric Fenton groove, 5-photo anode and foamy copper cathode bracket, 6-peristaltic pump.
FIG. 3 is a graph comparing the degradation effects of the method of the present invention on bisphenol A, a phenolic contaminant.
FIG. 4 is a graph comparing the degradation effects of the method of the present invention on a phenolic contaminant, p-hydroxyphenyl hydantoin.
FIG. 5 is a graph comparing the effect of different compositions of photoanode materials in the present invention on degradation of bisphenol A, a phenolic contaminant.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1
Preparation of Ag/TiO 2/BiFeO3 photo-anode:
34g (0.1 mol) of butyl titanate is dissolved in 46g (1 mol) of absolute ethyl alcohol to form butyl titanate ethanol solution, and the butyl titanate ethanol solution is dropwise added into 100g of ethanol water solution with the mass fraction of 70% of 1mol/L of nitric acid, and the acid nano TiO 2 ethanol hydrosol is formed through hydrolysis; 11.5g (0.03 mol) of bismuth nitrate and 7.3g (0.03 mol) of ferric nitrate are dissolved in an aqueous solution containing 19.2g (0.1 mol) of citric acid to obtain hydrosol of nano bismuth ferrite precursor; mixing the hydrosol of the nano bismuth ferrite precursor with the ethanol hydrosol of the nano TiO 2; then adding 1.7g (0.01 mol) of aqueous solution containing silver nitrate, and aging for 12 hours to form photo-anode coating hydrosol.
Cutting a titanium plate with the thickness of 1.5 mm into a strip with the thickness of 50mm multiplied by 200mm to serve as a collector substrate, bending the collector substrate into a concave inclined plate shape capable of focusing, polishing the surface to be bright by sand paper, dipping and coarsening the collector substrate by using a mixed aqueous solution of 3mol/L nitric acid and 0.3mol/L ammonium fluoride, washing the collector substrate by water and drying the collector substrate; coating photo-anode coating hydrosol on a titanium plate collector, and repeatedly coating for 5 times after the surface is solidified until the thickness of a surface wet film is more than 5 mu m; placing the solidified film-coated titanium plate collector into a high-temperature furnace, heating to 600 ℃, carrying out heat preservation and sintering for 2 hours, forming an Ag/TiO 2/BiFeO3 photo-anode with excellent surface hydrophilicity, adsorption performance and conductivity on a collector substrate, wherein the thickness of a surface photoelectrocatalysis film layer is 5 mu, the weight of the collector substrate is increased by 0.3g, and the mass composition of the surface film layer is as follows: ag6% and TiO 243%,BiFeO3%.
Example 2
Comparison of degradation effects of bisphenol A, a phenolic contaminant:
Adding 1000mL of bisphenol A wastewater with the concentration of 50mg/L into a photoelectric Fenton tank, regulating the pH value of the aqueous solution to be 3-6, adding 0.25g (2.2 mmol) of 30% H 2O2 oxidant aqueous solution, carrying out oxidation treatment for 2H under the 5 conditions listed in table 1, sampling every 20 minutes, and measuring the change of the concentration of bisphenol A in the photoelectric Fenton tank along with the oxidation reaction time by using a liquid chromatography method, wherein the degradation effect of bisphenol A pollutants in the phenol wastewater under different oxidation modes is shown as an attached figure 3 in the specification; the concentration change rate of bisphenol A pollutants in the phenolic wastewater under different oxidation conditions during the oxidation treatment for 2 hours is shown in table 1.
TABLE 1 concentration change Rate of bisphenol A contaminants in phenolic wastewater under different Oxidation conditions
| Sequence number | Oxidation reaction | Reaction characteristics | Bisphenol A concentration change rate at 120 min% |
| 1 | No light anode is irradiated, H 2O2 is not added, and the two electrodes are communicated | No oxidation reaction | ≤3 |
| 2 | Adding H 2O2 into the non-light-irradiated photo-anode, and connecting the two electrodes | Fenton-like oxidation | 32 |
| 3 | Visible light irradiates the photo-anode, H 2O2 is not added, and the two electrodes are communicated | Photoelectrocatalytic oxidation | 38 |
| 4 | Visible light irradiates the photo-anode, H 2O2 is added, and the two electrodes are disconnected | Photo Fenton oxidation | 72 |
| 5 | Visible light irradiates the photo-anode, H 2O2 is added, and the two electrodes are communicated | Photoelectric Fenton oxidation | 88 |
As can be seen from table 1, the light irradiation contributed about 56% to the change in bisphenol a contaminant concentration; the contribution of Fenton oxidation of H 2O2 class to bisphenol A contaminant concentration variation is about 32%; photo-anodic oxidation contributes approximately 22% to bisphenol a contaminant concentration variation; the copper foam cathode reduction contributed about 16% to the change in bisphenol a contaminant concentration.
Example 3
Comparison of degradation effects of phenolic pollutants, parahydroxyphenyl hydantoin:
1000mL of p-hydroxyphenyl hydantoin wastewater with the concentration of 500mg/L is added into a photoelectric Fenton tank, the pH value of the aqueous solution is regulated to be 3-6, 3.0g (26 mmol) of 30% H 2O2 oxidant aqueous solution is added, the oxidation treatment is carried out for 2H under 5 conditions, sampling is carried out every 20min, the change of the p-hydroxyphenyl hydantoin concentration in the photoelectric Fenton tank along with the oxidation reaction time is measured by a liquid chromatography method, and the degradation effect of p-hydroxyphenyl hydantoin pollutants in the phenolic wastewater under different oxidation modes is shown in an attached drawing 4 of the specification. The concentration change rate of the p-hydroxyphenyl hydantoin pollutants in the phenolic wastewater during the oxidation treatment for 2 hours is shown in table 2.
TABLE 2 concentration change Rate of P-hydroxyphenyl hydantoin pollutants in phenolic wastewater under different Oxidation conditions
As can be seen from table 2, the light irradiation contributed about 57% to the change in concentration of p-hydroxyphenyl hydantoin contaminants; class H 2O2 Fenton oxidation contributes approximately 35% to the change in concentration of p-hydroxyphenyl hydantoin contaminants; photo-anodic oxidation contributes about 26% to changes in concentration of p-hydroxyphenyl hydantoin contaminants; the copper foam cathode reduction contributes approximately 14% to the change in concentration of the p-hydroxyphenyl hydantoin contaminant.
Comparative example 1
Photo-anode materials with different compositions are used for degrading phenolic pollutants, namely bisphenol A effect comparison:
Adding 1000mL of bisphenol A wastewater with the concentration of 50mg/L into a photoelectric Fenton tank, adjusting the pH value of the aqueous solution to be 3-6, adding 0.25g of aqueous solution of 30% H 2O2 oxidant, changing the composition of photo-anode coating liquid to prepare photo-anodes of different materials, connecting the photo-anodes with a copper foam cathode, irradiating the photo-anodes with a 150W xenon lamp light source at a distance of 200mm, sampling every 10 minutes, detecting the concentration of bisphenol A in the phenolic wastewater by using liquid chromatography, and comparing the photo-anode photoelectric Fenton degradation bisphenol A pollutant effects of the photo-anodes with different material compositions, as shown in an attached drawing 5 of the specification. The concentration change rate of the photoanode degradation of bisphenol A pollutants in the phenolic wastewater of different materials is shown in Table 3.
TABLE 3 concentration change Rate of bisphenol A pollutants in different Material photo-anode degradation phenolic wastewater
As can be seen from Table 3, the concentration change rate of the Ag/TiO 2/BiFeO3 photo-anode material is increased by 30% -50% compared with that of the binary composite material photo-anode photo-Fenton oxidation bisphenol A, and the main reason is that the light absorption range is widened by compounding and doping of the three materials, so that the compounding of photo-generated electrons and holes on the photo-anode can be well inhibited.
According to the examples and the comparative examples, the combination of the photoelectrocatalysis technology and the Fenton-like oxidation technology has the effect of synergistically degrading phenolic pollutants in wastewater. If the photo-anode is connected with the foam copper cathode, the degradation effect is equivalent to photo-Fenton oxidation on the surface of the photo-anode, electro-Fenton oxidation is carried out on the surface of the foam cathode, and the composition of the photo-anode film has great influence on the degradation effect.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (4)
1. A method for degrading phenolic pollutants in industrial wastewater by using photoelectric Fenton is characterized in that a photoelectric catalytic oxidation technology and a Fenton-like oxidation technology are combined into a novel photoelectric Fenton technology, the generating capacity and pollutant degradation capacity of an oxidant OH are synergistically improved under visible light irradiation, and the phenolic pollutants in the industrial wastewater are efficiently degraded, wherein the method comprises four parts of preparation of photo-anode coating hydrosol, preparation of Ag/TiO 2/BiFeO3 photo-anode, construction of a photoelectric Fenton wastewater treatment system and degradation of the phenolic pollutants in the industrial wastewater;
the preparation method of the photo-anode coating hydrosol comprises the following specific steps:
S1: dissolving butyl titanate in absolute ethyl alcohol to form butyl titanate ethanol solution, dripping the butyl titanate into nitric acid ethanol water solution, hydrolyzing to form acidic nano TiO 2 ethanol hydrosol,
S2: bismuth nitrate and ferric nitrate are dissolved in aqueous solution of citric acid to obtain nano bismuth ferrite precursor hydrosol,
S3: mixing nano bismuth ferrite precursor hydrosol with acidic nano TiO 2 ethanol hydrosol, adding silver nitrate aqueous solution, and aging for 12-24h to form photoanode coating aqueous sol;
the preparation method of the Ag/TiO 2/BiFeO3 photo-anode comprises the following specific steps:
(1) Cutting titanium plate collector into concave inclined plate shape capable of focusing, polishing with sand paper to brightness, soaking with mixed aqueous solution of nitric acid and ammonium fluoride for coarsening, washing with water, drying to obtain photo-anode collector,
(2) Coating photo-anode coating hydrosol on a titanium plate collector, repeating the coating for 3-5 times after gel drying and curing until the thickness of a surface wet film is 5-10 mu m,
(3) Placing the solidified film-coated titanium plate collector electrode into a high-temperature furnace, heating to 500-700 ℃, and carrying out heat preservation and sintering for 1-4h to form an Ag/TiO 2/BiFeO3 photo-anode;
the construction method of the photoelectric Fenton wastewater treatment system comprises the following specific steps of:
step one: the photoelectric Fenton reaction tank, the H 2O2 metering tank, the alkali solution metering tank and the xenon lamp light source are assembled to construct the photoelectric Fenton wastewater treatment system, the core part is the photoelectric Fenton reaction tank,
Step two: a light anode in the shape of a concave inclined plate capable of condensing light is fixed in the photoelectric Fenton groove at an angle of 45 °-70° degrees,
Step three: fixing a foam copper cathode with the same concave inclined plate shape, and communicating the photo anode with the foam copper cathode through a switch and a lead;
The specific steps of degrading phenolic pollutants in industrial wastewater are as follows:
T1: injecting 0.05-0.5g/L phenolic wastewater into the photoelectric Fenton tank, immersing 1/5-1/3 height photo-anode and foam copper cathode,
T2: the peristaltic pump is used for circularly spraying phenolic wastewater in the photoelectric Fenton groove to the upper end of the photo-anode, a liquid film of 10-100 mu m is formed on the surface of the photo-anode, the photo-anode is irradiated by visible light emitted by a xenon lamp,
T3: the peristaltic pump is used for circularly spraying phenolic wastewater in the photoelectric Fenton tank to the upper end of the foam copper cathode, a liquid film with the flow velocity of 1-3m/s is formed on the surface of the foam copper cathode,
T4: adding sodium hydroxide aqueous solution to maintain the pH=3-7 of the phenolic wastewater in the photoelectric Fenton tank,
T5: adding H 2O2 water solution into the phenolic wastewater to make the initial concentration of H 2O2 in the phenolic wastewater be 0.05-1.0g/L,
T6: and (5) periodically sampling and measuring the concentration of the phenolic pollutants in the phenolic wastewater, and calculating the change rate of the concentration of the phenolic pollutants in the phenolic wastewater.
2. The method for photoelectric Fenton degradation of phenolic pollutants in industrial wastewater according to claim 1, wherein the molar ratio of butyl titanate, ethanol and nitric acid in step S1 is 1:10-30:0.1 to 0.5, wherein the molar ratio of bismuth nitrate, ferric nitrate and citric acid in the step S2 is 1:1:2-4, wherein the molar ratio of bismuth nitrate, ferric nitrate, butyl titanate and silver nitrate in the step S3 is 1:1:3-4:0.2-0.4.
3. The method for degrading phenolic pollutants in industrial wastewater by using photo-Fenton according to claim 1, wherein the surface film thickness of the Ag/TiO 2/BiFeO3 photo-anode obtained in the step (3) is 3-5 mu m.
4. A method for the photoelectric Fenton degradation of phenolic pollutants in industrial wastewater according to claim 3, wherein the mass composition of the surface film is as follows: 3-6% of Ag and 45-60% of TiO 235%-50%,BiFeO3.
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| CN108190997A (en) * | 2017-12-08 | 2018-06-22 | 浙江工业大学 | A kind of intensive control method of photoelectricity Fenton pretreatment tea polyphenols pharmacy waste water |
| US20190329236A1 (en) * | 2018-04-27 | 2019-10-31 | Soochow University | Loaded multifunctional catalysis composite material, preparation method thereof and application of composite material to catalytic removal of water pollutants |
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| CN104941662A (en) * | 2015-06-15 | 2015-09-30 | 桂林理工大学 | Preparation method of Ag/BFeO3 compound photocatalyst |
| CN108190997A (en) * | 2017-12-08 | 2018-06-22 | 浙江工业大学 | A kind of intensive control method of photoelectricity Fenton pretreatment tea polyphenols pharmacy waste water |
| US20190329236A1 (en) * | 2018-04-27 | 2019-10-31 | Soochow University | Loaded multifunctional catalysis composite material, preparation method thereof and application of composite material to catalytic removal of water pollutants |
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