CN110921789B - Preparation method of composite micro-electrolysis filler and method for treating wastewater - Google Patents
Preparation method of composite micro-electrolysis filler and method for treating wastewater Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a preparation method of a composite micro-electrolysis filler and a method for treating wastewater. The composite micro-electrolysis filler prepared by the method can react with oxygen to generate H in situ in the using process2O2And Fenton oxidation reaction is carried out, so that H faced by the conventional micro-electrolysis filler combined with Fenton oxidation at present is solved2O2The invention has the advantages of simple formula, low sintering temperature, capability of reacting with dissolved oxygen in water at normal temperature and normal pressure to generate strong oxidizing species such as hydrogen peroxide, hydroxyl free radical and the like, effective degradation of organic pollutants in water and obvious economic benefit and environmental benefit. Therefore, the method disclosed by the invention is simple to operate, convenient to prepare, environment-friendly, low in cost and suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a composite micro-electrolysis filler and a wastewater treatment method.
Background
The microelectrolysis technology is also called internal electrolysis technology, and its main technical principle is that the iron-carbon microelectrolysis filler is immersed in the waste water, and because of the electrode potential difference between iron and carbon, several corrosion microbatteries can be formed in the waste water, in which the iron with low potential is used as cathode and the carbon with high potential is used as anode. The micro batteries take the waste water as an electrolyte solution, generate electrochemical electrode reaction, generate active electrode products such as nascent state H and the like, and can generate oxidation-reduction reaction with organic pollutants in the waste water to degrade and remove the organic pollutants; meanwhile, iron ions generated in the electrode reaction process can further remove organic pollutants in water through flocculation and adsorption. The technology is widely applied to the treatment of organic wastewater with high chroma, high salt content and difficult biodegradation.
The iron-carbon micro-electrolysis filler is a key factor influencing the wastewater treatment effect of the micro-electrolysis technology. The traditional micro-electrolysis filler is generally iron chips and charcoal, the iron and the charcoal are in physical contact, acid and alkali are added for activation before use, and in the process of electrode reaction, electrons are difficult to effectively transfer and the effect is poor. In recent years, people can enhance the contact between iron and carbon through high-temperature sintering, and can improve the electrode reaction efficiency in the use process of the micro-electrolysis filler. Nevertheless, the modified iron-carbon microfiller still generates few kinds and quantities of active species in the wastewater treatment process, and has poor degradation efficiency on organic pollutants. This makes many waste water after micro-electrolysis treatment still need to utilize iron ion produced in water to add H2O2The effective degradation of the organic pollutants can be realized only by Fenton oxidation under the condition of (1). Addition of H2O2Not only causes high medicament cost, but also H2O2The easily decomposable nature poses a safety risk in its transport and storage. How to improve the degradation efficiency of organic pollutants by utilizing the micro-electrolysis combined with the Fenton oxidation process is a difficulty in the development of micro-electrolysis fillers at present. Therefore, the research and development of a novel, efficient and simple-to-operate micro-electrolysis filler which can generate H in situ in the using process is urgently needed2O2And carrying out a micro-electrolysis technology of Fenton oxidation reaction to treat the wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for generating H in situ by reacting with oxygen in use2O2The preparation and application method of the novel micro-electrolysis filler which generates Fenton oxidation reaction solves the problem of H faced by the conventional micro-electrolysis filler combined with Fenton oxidation at present2O2High cost of the medicament and difficult transportation and storage.
The purpose of the invention is realized by the following technical scheme: a preparation method of a composite micro-electrolysis filler is prepared by the following steps:
adding an iron-carbon compound and a copper salt into deionized water, carrying out displacement and oxidation reaction for 5-15 min under the conditions that the temperature is 40-60 ℃, the dissolved oxygen concentration is 0.1-6 mg/L, and the stirring rate is 150-250 r/min, carrying out solid-liquid separation on the solution after the reaction, and freeze-drying the obtained solid for 2-4 h under the conditions that the temperature of a cold trap is-40-80 ℃ and the vacuum degree is 1-10 Pa to obtain the composite micro-electrolysis filler.
Further, the iron-carbon composite is prepared by the following method: uniformly mixing iron salt, tannic acid and a conductive carbon material, putting the mixture into a high-energy ball milling tank, ball milling the mixture under the protection of argon by taking zirconium balls with the particle size of 3-6 mm as a grinding medium, wherein the ball milling speed is 400-800 r/min, the ball milling time is 2-4 h, putting a ball-milled sample into a tube furnace, sintering the ball-milled sample for 1.5-3 h under the conditions that the temperature is 450-650 ℃ and the argon flow rate is 80-120 ml/min, and cooling the mixture to room temperature to obtain the iron-carbon composite.
Further, the iron salt is ferric chloride or ferric sulfate, and the conductive carbon material is any one of carbon nanotubes, graphite or carbon black.
Further, the mass ratio of the iron salt to the tannic acid to the conductive carbon material is 1-10: 1: 1.
Further, the ratio of the mass of the zirconium balls to the sum of the mass of the iron salt, the tannic acid and the conductive carbon material is 30-100: 1.
Further, the copper salt is copper sulfate or copper chloride.
Further, the mass ratio of the iron-carbon composite to the copper salt is 1-10: 1.
Adding the composite micro-electrolysis filler into organic wastewater, adjusting the pH value of the wastewater to 1.5-4, reacting under the conditions of introducing oxygen and stirring, adjusting the pH value of a mixed solution to 6-9 after the reaction is finished, and performing solid-liquid separation to obtain supernatant, namely treated effluent.
Further, the mass ratio of the addition amount of the composite micro-electrolysis filler to COD in the wastewater is 10-300: 1.
Further, the reaction temperature is 10-30 ℃, the reaction time is 2-4 h, the stirring speed is 120-250 r/min, and the amount of introduced oxygen is 0.01-0.07 kg/m3*min。
The principle of the invention is as follows: when the iron salt, the tannic acid and the conductive carbon material are put into a ball milling tank according to a certain proportion and ball milling is carried out under the protection of argon, on one hand, the uniform mixing of the iron salt and the conductive material is promoted; on the other hand, during ball milling, carbon atom valence bonds on the surface of the carbon material are broken to form defect carbon, the defect carbon is easily combined at one end of tannic acid, while ferric salt can be combined with the other end of tannic acid through complexation, and through the complexation, the tannic acid bonds ferric salt and carbon together. When the iron-carbon binder is sintered at high temperature, trivalent iron is reduced to zero-valent iron by carbon and then forms a welding interface with the carbon, and meanwhile, tannic acid is decomposed into gas, so that a porous structure is formed at the iron-carbon interface. When the sintered iron-carbon composite and the copper salt are put into deionized water in the presence of micro oxygen, a small part of zero-valent iron in the iron-carbon composite reduces copper ions in the water into cuprous oxide to be loaded on the iron-carbon composite, and the composite micro-electrolysis filler containing iron, carbon and cuprous oxide is obtained after solid-liquid separation and freeze drying of solid.
When the microelectrolysis filler is put into organic wastewater, countless corrosion batteries can be formed in the water, iron as an anode loses electrons and generates ferrous iron, the electrons are easily transferred from the surface of the anode to the surface of the conductive carbon because the iron atoms and the carbon atoms form a welding interface in the composite microelectrolysis filler, and when a large amount of oxygen exists in the solution, the oxygen can diffuse to the surface of the conductive carbon to obtain the electrons to be reduced. Since conductive materials such as carbon nanotubes, graphite, and carbon black have excellent catalytic activity for 2-electron reduction of oxygen, oxygen is reduced to H on the surface of these conductive carbons2O2. And H generated in situ in solution2O2Can be catalyzed and decomposed into strong oxidizing species such as hydroxyl free radical (OH) and the like by ferrous iron in the solution and cuprous oxide in the composite electrolytic filler, and can oxidize, degrade and remove organic pollutants in water; meanwhile, ferrous iron in the solution is oxidized into ferric iron, and the ferric iron can further remove organic pollutants in water through flocculation and adsorption. Although cuprous oxide in the composite micro-electrolysis filler is used for catalytically decomposing H2O2Oxidized into bivalent copper, but the generated bivalent copper is compounded to be microelectron under the aerobic conditionZero-valent iron in the filler is reduced into cuprous oxide, so that the catalytic activity of the composite material is maintained, and the copper residue in the treated effluent is avoided. The relevant reactions involved are as follows:
(1) iron salts reduced by carbon at high temperatures
(2) Reaction of composite microelectrolytic filler with oxygen-containing water
Anode: fe0-2e-→Fe2+
Cathode: o is2+4H++e-→2H2O2
(3) Fenton oxidation reaction
Fe2++H2O2→·OH+Fe3+
Cu(I)+H2O2→·OH+Cu(II)
OH + organics → CO2+H2O
The invention has the following advantages:
(1) the invention makes full use of the reduction action of metal salt and conductive carbon at high temperature to form a welding interface between zero-valent iron and conductive carbon, thereby not only ensuring the effective transmission of electrons in the use process of the micro-electrolysis filler, but also greatly reducing the sintering temperature;
(2) compared with the traditional method for preparing the iron-carbon microfiller which requires the sintering temperature to be higher than 1300 ℃, the sintering temperature of the method is lower than 650 ℃, so that the energy consumption is greatly saved;
(3) the composite micro-electrolysis filler prepared by the invention has a porous structure, is beneficial to oxygen diffusion, and also contains a catalyst for reducing oxygen into H2O2Can selectively reduce oxygen introduced into water into H2O2To realize H in water2O2Is efficiently generated in situ. In combination with traditional microelectrolytic fillers to add H2O2Compared with Fenton oxidation reaction, the method greatly saves H2O2The cost of the medicament is enhanced2O2Safety of use;
(4) the micro-electrolysis filler prepared by the invention can realize H in water only by putting the micro-electrolysis filler into water with dissolved oxygen2O2The method has the advantages of simple operation, convenient preparation, environmental protection, low cost and suitability for industrial large-scale production.
Detailed Description
The invention is further described below with reference to examples, without limiting the scope of the invention to the following:
example 1: a preparation method of a composite micro-electrolysis filler is prepared by the following steps:
adding an iron-carbon compound and a copper salt into deionized water, wherein the mass ratio of the iron-carbon compound to the copper salt is 1:1, carrying out displacement and oxidation reaction for 5min under the conditions that the temperature is 40 ℃, the dissolved oxygen concentration is 0.1mg/L and the stirring speed is 150r/min, carrying out solid-liquid separation on the solution after the reaction, and carrying out freeze drying on the obtained solid for 2h under the conditions that the temperature of a cold trap is-40 ℃ and the vacuum degree is 1Pa, thus obtaining the composite micro-electrolysis filler.
The iron-carbon composite is prepared by the following method: uniformly mixing ferric salt chloride, tannic acid and carbon nano tubes of conductive carbon materials, putting the mixture into a high-energy ball milling tank, taking zirconium balls with the particle size of 3mm as a grinding medium, carrying out ball milling under the protection of argon, wherein the mass ratio of the ferric salt to the tannic acid to the conductive carbon materials is 1:1:1, the mass ratio of the zirconium balls to the sum of the ferric salt to the tannic acid to the conductive carbon materials is 30:1, the ball milling speed is 400r/min, the ball milling time is 2h, putting a ball-milled sample into a tube furnace, sintering for 1.5h under the conditions that the temperature is 450 ℃ and the argon gas flow rate is 80ml/min, and cooling to room temperature to obtain the iron-carbon composite.
Example 2: a preparation method of a composite micro-electrolysis filler is prepared by the following steps:
adding an iron-carbon compound and copper salt into deionized water, wherein the mass ratio of the iron-carbon compound to the copper salt is 10:1, carrying out displacement and oxidation reaction for 15min under the conditions that the temperature is 60 ℃, the dissolved oxygen concentration is 6mg/L and the stirring speed is 250r/min, carrying out solid-liquid separation on the solution after the reaction, and carrying out freeze drying on the obtained solid for 4h under the conditions that the temperature of a cold trap is-80 ℃ and the vacuum degree is 10Pa, thus obtaining the composite micro-electrolysis filler.
The iron-carbon composite is prepared by the following method: uniformly mixing ferric salt ferric sulfate, tannic acid and conductive carbon material graphite, putting the mixture into a high-energy ball milling tank, taking zirconium balls with the particle size of 6mm as a grinding medium, carrying out ball milling under the protection of argon, wherein the mass ratio of the ferric salt to the tannic acid to the conductive carbon material is 10:1:1, the mass ratio of the zirconium balls to the sum of the ferric salt to the tannic acid to the conductive carbon material is 100:1, the ball milling rotation speed is 800r/min, the ball milling time is 4h, putting a ball-milled sample into a tube furnace, sintering for 3h under the conditions that the temperature is 650 ℃ and the argon gas flow rate is 120ml/min, and cooling to room temperature to obtain the iron-carbon composite.
Example 3: a preparation method of a composite micro-electrolysis filler is prepared by the following steps:
adding an iron-carbon compound and copper salt into deionized water, wherein the mass ratio of the iron-carbon compound to the copper salt is 5:1, carrying out displacement and oxidation reaction for 10min under the conditions that the temperature is 50 ℃, the dissolved oxygen concentration is 4mg/L and the stirring speed is 200r/min, carrying out solid-liquid separation on the solution after the reaction, and carrying out freeze drying on the obtained solid for 2.5h under the conditions that the temperature of a cold trap is-60 ℃ and the vacuum degree is 7Pa, thus obtaining the composite micro-electrolysis filler.
The iron-carbon composite is prepared by the following method: uniformly mixing ferric salt chloride, tannic acid and carbon black of a conductive carbon material, putting the mixture into a high-energy ball milling tank, taking zirconium balls with the particle size of 4mm as a grinding medium, carrying out ball milling under the protection of argon, wherein the mass ratio of the ferric salt to the tannic acid to the carbon black of the conductive carbon material is 7:1:1, the mass ratio of the zirconium balls to the sum of the ferric salt to the tannic acid to the carbon black of the conductive carbon material is 75:1, the ball milling speed is 600r/min, the ball milling time is 2.5h, putting a ball-milled sample into a tube furnace, sintering for 2h under the conditions that the temperature is 500 ℃ and the airflow speed is 100ml/min, and cooling to room temperature to obtain the iron-carbon composite.
Example 4: a method for treating wastewater comprises the steps of adding the composite micro-electrolysis filler prepared in the embodiment 1 into organic wastewater, adjusting the pH value of the wastewater to 1.5, reacting under the conditions of introducing oxygen and stirring, adjusting the pH value of a mixed solution to 6 after the reaction is finished, and carrying out solid-liquid separation to obtain supernatant, namely treated effluent.
Wherein the mass ratio of the addition amount of the composite micro-electrolysis filler to COD in the wastewater is 10: 1; the reaction temperature is 10 ℃, the reaction time is 2h, the stirring speed is 120r/min, and the amount of introduced oxygen is 0.01kg/m3*min。
Example 5: a method for treating wastewater comprises the steps of adding the composite micro-electrolysis filler prepared in the embodiment 2 into organic wastewater, adjusting the pH value of the wastewater to 4, reacting under the conditions of introducing oxygen and stirring, adjusting the pH value of a mixed solution to 9 after the reaction is finished, and carrying out solid-liquid separation to obtain supernatant, namely treated effluent.
Wherein the mass ratio of the addition amount of the composite micro-electrolysis filler to COD in the wastewater is 300: 1; the reaction temperature is 30 ℃, the reaction time is 4h, the stirring speed is 250r/min, and the amount of introduced oxygen is 0.07kg/m3*min。
Example 6: a method for treating wastewater comprises the steps of adding the composite micro-electrolysis filler prepared in the embodiment 3 into organic wastewater, adjusting the pH value of the wastewater to 3, reacting under the conditions of introducing oxygen and stirring, adjusting the pH value of a mixed solution to 7 after the reaction is finished, and carrying out solid-liquid separation to obtain supernatant, namely treated effluent.
Wherein the mass ratio of the addition amount of the composite micro-electrolysis filler to COD in the wastewater is 200: 1; the reaction temperature is 15 ℃, the reaction time is 3h, the stirring speed is 180r/min, and the amount of introduced oxygen is 0.05kg/m3Min. Experimental example 1: preparing the composite micro-electrolysis filler:
(1) FeCl with the mass ratio of 2:1:13·6H2Mixing O, tannic acid and carbon nano tube uniformly, placing into a high-energy ball milling tank, ball milling for 2h under the condition of ball-material mass ratio of 35:1 and argon protection and rotating speed of 420r/min by taking zirconium balls with particle size of 5mm as grinding media, placing the ball-milled sample into a tube furnace, and placing the strip in the tube furnace at the temperature of 500 ℃ and the argon flow rate of 100mL/minAnd sintering for 2 hours under the condition of a workpiece to obtain the iron-carbon composite.
(2) Adding the prepared iron-carbon composite into an acid-alkali resistant reaction bottle, adding 1L of water solution containing 0.15mg/L of oxygen, adding 0.3L of copper sulfate solution with the mass concentration of 3.3g/L, stirring for 10min under the conditions of constant temperature (30 ℃) of a water bath and the rotating speed of 200r/min, then washing to be neutral by deionized water, pouring out supernate, and freeze-drying the solid for 2.5h under the conditions that the temperature of a cold trap is-50 ℃ and the vacuum degree is 3Pa to prepare the composite micro-electrolysis filler.
The application of the composite micro-electrolysis filler comprises the following steps:
the secondary biological treatment effluent of domestic sewage in a certain town has COD concentration of 191.27mg/L in raw water, 2L of the wastewater is collected into a 3L acid-alkali-resistant container, hydrochloric acid is adopted to adjust the pH value of the wastewater to 2.0, 50g/L of composite micro-electrolysis filler is added into the container, and the amount of introduced oxygen is 0.044kg/(m3Min), reacting for 3h at a temperature of 20 ℃ and under stirring conditions (stirring rate of 220 r/min); after the reaction is finished, the pH value of the wastewater in the container is 4.6, sodium hydroxide is added into the container to adjust the pH value of the mixed solution to be 8, solid-liquid separation is carried out, and the supernatant is effluent. The COD content in the treated water is measured to be 6.95mg/L, and the removal rate of the COD reaches 96.4 percent.
Experimental example 2:
preparing the composite micro-electrolysis filler:
(1) FeCl with the mass ratio of 3:1:13·6H2Mixing O, tannic acid and carbon nano tubes uniformly, placing the mixture into a high-energy ball milling tank, ball milling for 2 hours by taking zirconium balls with the particle size of 6mm as a grinding medium under the conditions that the mass ratio of the balls to the materials is 35:1, argon protection and the rotating speed is 450r/min, and placing a ball-milled sample into a tube furnace to sinter for 1.5 hours under the conditions that the temperature is 600 ℃ and the argon flow rate is 80mL/min to obtain the iron-carbon composite.
(2) Adding the prepared iron-carbon composite into an acid-alkali resistant reaction bottle, adding 1L of water solution containing 1.5mg/L of oxygen, adding 0.3L of copper sulfate solution with the mass concentration of 6.6g/L, stirring for 10min under the conditions of constant temperature (40 ℃) of water bath and the rotating speed of 200r/min, then washing to be neutral by deionized water, pouring out supernate, and freeze-drying the solid for 4h under the conditions that the temperature of a cold trap is-60 ℃ and the vacuum degree is 10Pa to prepare the composite micro-electrolysis filler.
The application of the composite micro-electrolysis filler comprises the following steps:
the COD concentration of raw water in certain landfill leachate secondary biological treatment effluent is 624.6mg/L, 1.5L of the wastewater is collected into a 2.5L acid and alkali resistant container, the pH value of the wastewater is adjusted to 1.8 by adopting sodium hydroxide, 60g/L of composite micro-electrolysis filler is added into the container, and the amount of introduced oxygen is 0.032 kg/(m/L)3Min), reacting for 2.5h at a temperature of 20 ℃ and under stirring conditions (stirring rate of 150 r/min); after the reaction is finished, the pH value of the wastewater in the container is 3.5, sodium hydroxide is added into the container to adjust the pH value of the mixed solution to be 8.5, solid-liquid separation is carried out, and the supernatant is effluent. The COD content in the treated water is determined to be 73.7mg/L, and the removal rate of COD reaches 88.2 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and the inventive concept within the technical scope of the present invention.
Claims (9)
1. The preparation method of the composite micro-electrolysis filler is characterized by comprising the following steps:
adding an iron-carbon compound and a copper salt into deionized water, carrying out displacement and oxidation reaction for 5-15 min under the conditions that the temperature is 40-60 ℃, the dissolved oxygen concentration is 0.1-6 mg/L and the stirring rate is 150-250 r/min, carrying out solid-liquid separation on the solution after the reaction, and freeze-drying the obtained solid for 2-4 h under the conditions that the temperature of a cold trap is-40-80 ℃ and the vacuum degree is 1-10 Pa to obtain the composite micro-electrolysis filler;
the iron-carbon composite is prepared by the following method: uniformly mixing iron salt, tannic acid and a conductive carbon material, putting the mixture into a high-energy ball milling tank, ball milling the mixture under the protection of argon by taking zirconium balls with the particle size of 3-6 mm as a grinding medium, wherein the ball milling speed is 400-800 r/min, the ball milling time is 2-4 h, putting a ball-milled sample into a tube furnace, sintering the ball-milled sample for 1.5-3 h under the conditions that the temperature is 450-650 ℃ and the argon flow rate is 80-120 mL/min, and cooling the mixture to room temperature to obtain the iron-carbon composite.
2. The method of claim 1, wherein the iron salt is ferric chloride or ferric sulfate, and the conductive carbon material is any one of carbon nanotube, graphite or carbon black.
3. The preparation method of the composite micro-electrolysis filler according to claim 1, wherein the mass ratio of the iron salt to the tannic acid to the conductive carbon material is 1-10: 1: 1.
4. The preparation method of the composite micro-electrolysis filler according to claim 1, wherein the ratio of the mass of the zirconium balls to the sum of the mass of the iron salt, the tannic acid and the conductive carbon material is 30-100: 1.
5. The method of claim 1, wherein the copper salt is copper sulfate or copper chloride.
6. The preparation method of the composite micro-electrolysis filler according to claim 1, wherein the mass ratio of the iron-carbon composite to the copper salt is 1-10: 1.
7. A method for treating wastewater is characterized in that the composite microelectrolysis filler disclosed by any one of claims 1 to 6 is added into organic wastewater, the pH value of the wastewater is adjusted to 1.5-4, the wastewater reacts under the conditions of introducing oxygen and stirring, the pH value of a mixed solution is adjusted to 6-9 after the reaction is finished, solid-liquid separation is carried out, and supernatant is treated effluent.
8. The method for treating wastewater according to claim 7, wherein the mass ratio of the added amount of the composite micro-electrolysis filler to COD in the wastewater is 10-300: 1.
9. The method for treating wastewater according to claim 7, wherein the reaction temperature is 10-30 ℃, the reaction time is 2-4 h, the stirring speed is 120-250 r/min, and the amount of introduced oxygen is 0.01-0.07 kg/m3*min。
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| US20120285899A1 (en) * | 2011-05-12 | 2012-11-15 | T&H Usa Group, Inc. | Nanopolymetalic reducing agent filler |
| CN107686156A (en) * | 2017-10-25 | 2018-02-13 | 四川师范大学 | A kind of Fenton methods of efficient degradation organic pollutants |
| CN108771964A (en) * | 2018-06-21 | 2018-11-09 | 江苏大学 | A kind of nano cuprous oxide light electrolysis deodorization device |
| CN109110883A (en) * | 2018-09-21 | 2019-01-01 | 中国矿业大学(北京) | A kind of preparation of compound carbon-based nano zero valence iron micro-electrolysis material and the method for handling stibium-containing wastewater |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120285899A1 (en) * | 2011-05-12 | 2012-11-15 | T&H Usa Group, Inc. | Nanopolymetalic reducing agent filler |
| CN107686156A (en) * | 2017-10-25 | 2018-02-13 | 四川师范大学 | A kind of Fenton methods of efficient degradation organic pollutants |
| CN108771964A (en) * | 2018-06-21 | 2018-11-09 | 江苏大学 | A kind of nano cuprous oxide light electrolysis deodorization device |
| CN109110883A (en) * | 2018-09-21 | 2019-01-01 | 中国矿业大学(北京) | A kind of preparation of compound carbon-based nano zero valence iron micro-electrolysis material and the method for handling stibium-containing wastewater |
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