WO2018000795A1 - 一种废水处理用铁基非晶电极材料及其应用 - Google Patents

一种废水处理用铁基非晶电极材料及其应用 Download PDF

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WO2018000795A1
WO2018000795A1 PCT/CN2017/000224 CN2017000224W WO2018000795A1 WO 2018000795 A1 WO2018000795 A1 WO 2018000795A1 CN 2017000224 W CN2017000224 W CN 2017000224W WO 2018000795 A1 WO2018000795 A1 WO 2018000795A1
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iron
based amorphous
amorphous alloy
electrode
solution
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PCT/CN2017/000224
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English (en)
French (fr)
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朱正旺
秦鑫冬
张海峰
王爱民
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中国科学院金属研究所
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Priority claimed from CN201610489617.3A external-priority patent/CN107540054A/zh
Priority claimed from CN201610569480.2A external-priority patent/CN106006916B/zh
Application filed by 中国科学院金属研究所 filed Critical 中国科学院金属研究所
Priority to US16/309,309 priority Critical patent/US11027992B2/en
Priority to EP17818796.9A priority patent/EP3480342A4/en
Publication of WO2018000795A1 publication Critical patent/WO2018000795A1/zh

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/46135—Voltage

Definitions

  • the invention relates to an iron-based amorphous alloy material and an application thereof, in particular to an iron-based amorphous alloy as an electrode material for electrochemical wastewater treatment and its application in the field of industrial wastewater treatment.
  • refractory industrial wastewater treatment methods mainly include physical methods, biological methods and chemical methods.
  • the physical method mainly includes adsorption method, flocculation method, ultrafiltration method, etc.
  • the dosage of the flocculant is large, the sludge generated is large, the separation of the ultrafiltration method is difficult, and the like. Be optimistic.
  • the physical method only collects pollutants and does not achieve the purpose of truly degrading pollutants.
  • the biological method utilizes microbial enzymes to degrade pollutant molecules, especially organic pollutant molecules, but the microorganisms are harsh on the external environment, such as nutrients, temperature, pH, etc., and have complex components, high concentration of pollutants, and toxicity.
  • Electrochemical treatment technology has the advantages of high degradation efficiency, low secondary pollution, simple operation and so on. It has unique advantages in industrial wastewater degradation as an environmentally friendly treatment process. According to the principle of pollutant degradation, it can be subdivided into electrochemical redox, electrocoagulation, electrical floatation, photoelectrochemical oxidation, and internal electrolysis.
  • electrode material technology is one of the key ways to solve the above problems.
  • the development of electrode materials with high stability, high corrosion resistance and high electrocatalytic activity is an urgent need to promote the wide application of such technologies.
  • the object of the present invention is to provide a method for efficiently degrading industrial wastewater by using an iron-based amorphous alloy material as an electrode material, and the iron-based amorphous alloy strip as an electrode has good stability in electrochemical degradation of industrial wastewater. In order to achieve high degradation efficiency of industrial wastewater, it also greatly reduces electricity consumption.
  • An iron-based amorphous electrode material for wastewater treatment characterized in that the material is an iron-based amorphous alloy used as an electrode for electrochemically degrading industrial wastewater, and the atomic percentage of iron element in the alloy composition is 40 to 84%, Preferably, it is 65 to 84%, and the most preferable range is 70 to 84%, and other alloying elements are preferably one or more selected from the group consisting of Si, B, P, C, Mo, Nb, Cu, Ni, and Co.
  • a method for degrading industrial wastewater by using an iron-based amorphous alloy characterized in that an iron-based amorphous alloy strip is used as an electrode for electrochemically degrading industrial wastewater (preferably dye wastewater), and the electrode potential thereof is 0-5 V, flowing through it The current is 0.005A to 1A.
  • the atomic percentage of the iron element in the alloy composition is 40 to 84%, preferably 65 to 84%, and most preferably 70 to 84%.
  • the iron-based amorphous alloy strip used is prepared by an entrainment method with a strip thickness of 15 ⁇ m to 100 ⁇ m.
  • the specific surface area concentration of the iron-based amorphous alloy strip in the dye wastewater solution is greater than 100 cm 2 /(g ⁇ L).
  • the concentration of the dye wastewater solution is from 20 mg/L to 2000 mg/L, the temperature of the solution is from ambient temperature to 100 ° C, and the pH of the solution is from 1 to 12.
  • the dye wastewater is stirred by a stirrer at a rotation speed of 100 rpm to 800 rpm.
  • the present invention Compared with a conventional metal electrode such as aluminum or iron, a metal oxide electrode such as PbO 2 , the present invention has the following advantages:
  • the iron-based amorphous alloy strip of the present invention electrochemically degrades the azo dye as an electrode, which not only can achieve high degradation efficiency of the wastewater, but also can greatly reduce energy consumption.
  • the iron-based amorphous alloy strip has good stability and wide application range in degrading dye wastewater.
  • the uniformity of the composition of the iron-based amorphous alloy greatly reduces the corrosion rate of iron.
  • the strips after participating in the degradation of the dye wastewater can still maintain the amorphous structure, and the electrode quality loss is small, which provides a guarantee for recycling and reuse. Extends the life of the electrode.
  • the iron-based amorphous alloy according to the present invention has a wide source of sources. With the widespread use of amorphous transformers, iron-based amorphous alloy strips have been and will have more waste, including defective products produced during the processing of ribbons and transformers, and waste products produced after the transformer has reached the end of its useful life. and many more. The application of these discarded strips to the electrochemical degradation of dye wastewater can achieve the benefits of waste treatment. Not only is the price cheap, but it can also realize the integration and utilization of waste energy.
  • the electrochemical degradation dye wastewater provided by the invention has simple process, low production cost and good application prospect.
  • Fig. 1 is an XRD pattern of an iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%) before and after the reaction of degrading the acidic orange II solution.
  • FIG. 2 is a graph showing the ultraviolet-visible absorption spectrum of an acidic orange II solution as a function of reaction time under the electrochemical degradation of an iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%). And the curve of C t /C 0 with reaction time.
  • the electrode voltage was 0.5 V and the solution temperature was 60 °C.
  • FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum of an acidic orange II solution as a function of reaction time under the electrochemical degradation of Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%) of an iron-based amorphous alloy strip. And the curve of C t /C 0 with reaction time.
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Figure 4 is a graph showing the UV-visible absorption spectrum of an acidic orange II solution as a function of reaction time under the degradation of an iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%), and C.
  • the electrode voltage was 0 V and the solution temperature was 60 °C.
  • Degradation of the tape 5 is Fe 78 Si 8 B 14 in the Fe-based amorphous alloy article (at%.), And Acid Orange II solution UV - visible absorption spectrum curve with reaction time, and C t / C 0 The curve as a function of reaction time.
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Figure 6 is a graph showing the UV-visible absorption spectrum of an acidic orange II solution as a function of reaction time under the electrochemical degradation of an iron-based amorphous alloy strip Fe 83 Si 4 B 10 P 2 Cu 1 (at.%). And the curve of C t /C 0 with reaction time.
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Fig. 7 is a graph showing the change of C t /C 0 of the acid orange II solution with the reaction time under the electrochemical degradation of the iron-based amorphous alloy strip Fe 65 Co 13 Si 8 B 14 (at.%).
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Fig. 8 is a graph showing the change of C t /C 0 of the acid orange II solution with the reaction time under the electrochemical degradation of the iron-based amorphous alloy strip Fe 40 Co 38 Si 8 B 14 (at.%).
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Fig. 9 is a graph showing the change of C t /C 0 of the acid orange II solution with the reaction time under the electrochemical degradation of the Fe-based amorphous alloy strip Fe 68 Ni 10 Si 8 B 14 (at.%).
  • the electrode voltage was 1V and the solution temperature was 60 °C.
  • Fig. 10 is a graph showing the change of C t /C 0 of the acid orange II solution with the reaction time under the electrochemical degradation of the iron-based amorphous alloy strip Fe 50 Ni 28 Si 8 B 14 (at.%).
  • the electrode voltage was 1 V and the solution temperature was 60 °C.
  • Figure 11 is a photograph of a sample of the acid orange II solution before and after the reaction of the electrode of the iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%) with electrode voltages of 1 V and 0 V, respectively.
  • the invention utilizes the entrainment method to obtain iron-based amorphous alloy strips, mainly concentrated in Fe-B, Fe-Si-B, Fe-Co-Si-B, Fe-Ni-Si-B, Fe-Si-BP, Fe-Si-B-Mo, Fe-Si-B-Nb, Fe-Si-BP-Cu, Fe-Si-B-Nb-Cu, Fe-BC, Fe-BC-Nb, Fe-BC-Cu, Alloy system such as Fe-PC Fe-PC-Cu, typical nominal composition (atomic percentage) such as: Fe 83 B 17 , Fe 78 Si 8 B 14 , Fe 65 Co 13 Si 8 B 14 , Fe 40 Co 38 Si 8 B 14 , Fe 68 Ni 10 Si 8 B 14 , Fe 50 Ni 28 Si 8 B 14 , Fe 83 B 10 Si 4 P 3 , Fe 77 Si 8 B 14 Mo 1 , Fe 74.5 Nb 3 Si 13.5 B 9 , Fe 83 Si 4 B 10 P 2 Cu 1 , Fe 73.5
  • Figure 1 is an XRD pattern of Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%) of iron-based amorphous alloy strips before and after the reaction. There is no significant difference in the XRD patterns of the strips before and after the reaction. Crystal structure.
  • the iron-based amorphous alloy strip was used as an electrode to electrochemically degrade the acidic orange II solution.
  • the surface area of the electrode participating in the reaction was 50 cm 2 , the concentration of the acidic orange II solution was 0.2 g/L, and the volume of the solution was 300 mL.
  • the beaker containing the Acid Orange II solution was placed in an electromagnetic stirring system and the dye solution was stirred at 200 rpm, and the temperature was controlled at 60 °C.
  • the electrodes were tested at a voltage of 0.5 V and 1 V, respectively. After the start of the reaction, about 3 mL of the solution was taken out at intervals of time for ultraviolet-visible absorption spectroscopy.
  • the corresponding absorbance is proportional to the solubility of the solution, so it can be changed by the absorbance at the maximum absorption peak.
  • the solubility of the solution changes.
  • FIG. 2 is a graph showing the ultraviolet-visible absorption spectrum of an acidic orange II solution as a function of reaction time under the electrochemical degradation of an iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%).
  • the electrode voltage is 0.5V.
  • Figure 2b shows the kinetic curve of acid orange II degradation. After nonlinear fitting, it is found that the degradation process satisfies the pseudo first-order reaction:
  • the degradation efficiency of the acidic orange II solution can reach 90.42% when the reaction is 240min, and the rate constant obtained by the fitting is 0.014min -1 .
  • the calculated electrical energy consumption is 40.76J
  • the electrical energy consumption per unit degradation efficiency is 0.45J/%
  • the mass loss of the electrode is 16mg.
  • the degradation efficiency of acid orange II solution can reach 98.06%
  • the energy consumption is 91.65J
  • the energy consumption per unit degradation efficiency is 0.94J/ when the other experimental conditions are the same. %
  • the mass loss of the electrode was 60 mg.
  • the high-purity iron foil and the iron-based amorphous alloy strip have the same surface area, and the thickness of the iron foil (100 ⁇ m) is three times that of the iron-based amorphous alloy strip thickness (30 ⁇ m), and the iron-based amorphous alloy It contains a large amount of non-metallic elements. Therefore, the iron content per unit surface area of the iron-based amorphous alloy strip is much less than that of the high-purity iron foil.
  • the degradation efficiency of the acidic orange II can reach 90% when the iron-based amorphous alloy strip is used as the electrode.
  • the degradation efficiency of the iron-based amorphous alloy strip with the unit iron content as the electrode to the acidic orange II solution is certainly greater than that of the high-purity iron foil.
  • the energy consumption and electrode mass loss of the high-purity iron foil as the electrode far exceeds that of the iron-based amorphous alloy strip, and it can be seen that the iron-based amorphous alloy strip acts as an electrode for electrochemically degrading the acidic orange II solution as compared with the high-purity iron foil. It has the advantages of high degradation efficiency, less electrode loss, long electrode life and low energy consumption.
  • Figure 3 shows the degradation process of the acidic orange II solution when the electrode voltage is increased to 1 V under the electrochemical degradation of Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%).
  • the degradation efficiency can reach 92.67%, and at 60 min, it can reach 96.60%. It can be seen that the electrode voltage increases to a certain extent to contribute to the degradation of Acid Orange II.
  • Fig. 4 shows the degradation of the acidic orange II solution when the Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%) electrode of the iron-based amorphous alloy strip is in an open state. It can be seen that the degradation of acid orange II is very slow in the absence of electrochemistry, and the degradation efficiency is only 25.34% and the reaction rate constant is 0.006 min -1 when the reaction is carried out for 300 min. It can be seen that under electrochemical action, the reaction rate and degradation efficiency of the iron-based amorphous alloy strip degrading the acidic orange II solution are far greater than those without electricity.
  • Fig. 5 is a diagram showing the degradation process of the acidic orange II solution under the electrochemical degradation of Fe 78 Si 8 B 14 (at.%) of the iron-based amorphous alloy strip at an electrode voltage of 1V.
  • the degradation efficiency can reach 95.47%.
  • the degradation efficiency can reach 98.46%. It can be seen that with the increase of Fe content in the iron-based amorphous alloy, the degradation rate of acid orange II is accelerated.
  • Fig. 6 is a diagram showing the degradation process of the acidic orange II solution under the electrochemical degradation of the Fe-based amorphous alloy strip Fe 83 Si 4 B 10 P 2 Cu 1 (at.%). When the reaction was carried out for 18 min, the degradation efficiency was 97.32%, and the reaction rate constant was 0.295 min -1 .
  • Fig. 7 is an electrochemically degraded acid orange II solution of Fe 65 Co 13 Si 8 B 14 (at.%) in an iron-based amorphous alloy strip.
  • the degradation efficiency is 96.19% and the reaction rate constant is 0.225 min -1 when reacted for 20 min.
  • Fig. 8 is an electrochemically degraded acid orange II solution of Fe-based amorphous alloy strip Fe 40 Co 38 Si 8 B 14 (at.%).
  • the degradation efficiency was 97.94% and the reaction rate constant was 0.435 min -1 when reacted for 14 min. It can be seen that the small addition of Co in the Fe-based amorphous alloy does not significantly affect the degradation effect, while the increase in the content of Co accelerates the rate of electrochemical degradation of the iron-based amorphous alloy strip.
  • FIG. 9 shows that the iron-based amorphous alloy strip Fe 68 Ni 10 Si 8 B 14 (at.%) electrochemically degrades acidic orange II.
  • the degradation efficiency is 96.19%, and the reaction rate constant is 0.217 min -1 .
  • Figure 10 shows the electrochemical degradation of acid orange II by Fe 50 Ni 28 Si 8 B 14 (at.%). The degradation efficiency is 95.67% and the reaction rate constant is 0.327min -1 .
  • Figure 11 is a sample photograph of the acid orange II solution before and after the reaction of the electrode of the iron-based amorphous alloy strip Fe 73.5 Nb 3 Cu 1 Si 13.5 B 9 (at.%), the electrode voltage is 1V and 0V, respectively. It can be seen that under the action of electrochemistry, the reaction is changed from initial orange red to colorless and transparent state for 60 min, and when there is no electrochemical action, the reaction is for 300 min, and the color of the solution hardly changes significantly.
  • the technical solution is basically the same as the embodiment, and the composition of the iron-based amorphous alloy is Fe 78 Si 8 B 14 (at.%), except that the current example does not apply current and voltage, and the remaining technical details are the same as the embodiment.
  • the test results show that it takes 120min to effectively degrade the azo dye, and the decolorization efficiency is 96.09%. Obviously, by comparison, it can be found that the decoloring effect of the technical solution of the present invention is greatly enhanced.
  • the iron-based amorphous alloy strip as an electrode electrochemically degrades the acidic orange II solution, which has the advantages of high degradation efficiency, less electrode loss, long electrode life and low electric energy consumption.

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Abstract

一种工业废水处理用铁基非晶电极材料，材料为铁基非晶合金，作为电极用于电化学降解工业废水，该合金成分中铁元素的原子百分比在40～84％。以及一种铁基非晶电极材料处理染料废水的方法，和铁基非晶电极材料在电化学降解工业废水方面的应用。

Description

一种废水处理用铁基非晶电极材料及其应用 技术领域
本发明涉及铁基非晶合金材料及其应用，具体涉及一种铁基非晶合金作为电化学废水处理用电极材料及其在工业废水处理领域的应用。
背景技术
随着工业的迅猛发展，排放的废水的种类和数量快速增加，对水体的污染也日趋广泛和严重，已严重威胁人类的健康和安全。因此，对于保护环境和可持续发展而言，工业废水的处理比城市污水的处理更为重要。目前，难降解工业废水处理方法主要有物理法、生物法和化学法等。物理法主要包括吸附法、絮凝法、超滤法等，然而由于吸附剂的不可再生、价格昂贵，絮凝剂的投加量大、产生的淤泥多，超滤法的分离困难等等原因而不被看好。而且物理法仅仅是将污染物收集起来，并未达到真正降解污染物的目的。生物法是利用微生物酶对污染物分子，特别是有机污染物分子进行降解，但由于微生物对外界环境，如营养物质、温度、pH等要求较为苛刻，且对成分复杂、污染物浓度高、毒性大的染料废水抵抗力低等缺点而限制了其广泛应用。电化学处理技术具有降解效率高、二次污染低、运行操作简单等优点，其作为环境友好型处理工艺在工业废水降解中有独特的优势。根据污染物降解原理不同，又可细分为电化学氧化还原、电凝聚、电气浮、光电化学氧化、内电解等。然而能耗高、电极损耗严重、稳定性差成为制约电化学技术处理工业废水的共性问题。因此，电极材料技术是解决以上问题的关键途径之一。研制高稳定性、高耐蚀、高电催化活性的电极材料是推动这类技术广泛应用的急需。
非晶合金长程无序、短程有序的结构特征以及体系处于的高能量状态赋予其优异的化学以及催化性能，同时由于成分的均匀性，相比晶态合金而言，具 有更高的耐蚀性。已有文献报道将铁基非晶合金条带作为一种内电解材料放入染料废水中，均匀搅拌，可以实现脱色效果。与传统零价铁方法相比，铁基非晶合金的脱色效率明显提高。然而，针对于实际应用，铁基非晶合金的处理效率相对较低和质量损失大仍然是亟待解决的关键问题。如何充分发挥铁基非晶合金的性能优势，开发一种高效、稳定、低成本的工业废水处理技术，是当前迫切需要解决的问题。
发明内容
本发明的目的在于提供一种利用铁基非晶合金材料作为电极材料高效降解工业废水的方法，该铁基非晶合金条带作为电极在电化学降解工业废水的过程中具有很好的稳定性，在使工业废水达到很高降解效率的同时，还大大降低了电能耗。
本发明的技术方案如下：
一种废水处理用铁基非晶电极材料，其特征在于：所述材料为铁基非晶合金，作为电极用于电化学降解工业废水，该合金成分中铁元素的原子百分比在40～84％，优选65～84％，最优选范围是70～84％，其他合金元素优选自Si、B、P、C、Mo、Nb、Cu、Ni、Co中一种或几种。
一种利用铁基非晶合金降解工业废水的方法，其特征在于：采用铁基非晶合金条带作为电极电化学降解工业废水(优选染料废水)，其电极电位为0～5V，流过其的电流为0.005A～1A。合金成分中铁元素的原子百分比在40～84％，优选65～84％，最优选范围70～84％。
采用的铁基非晶合金条带通过甩带法制备，条带厚度为15μm～100μm。
所述的铁基非晶合金条带在染料废水溶液中的比表面积浓度大于100cm2/(g·L)。
所述染料废水溶液的浓度为20mg/L～2000mg/L，溶液的温度为环境温度到100℃，溶液的pH值为1～12。
所述的铁基非晶合金降解染料废水的方法中，通过搅拌器以100rpm～800rpm的转速对染料废水进行搅拌。
相对于传统的铝、铁等金属电极，PbO2等金属氧化物电极，本发明具有以下优点：
1.本发明所述的铁基非晶合金条带作为电极电化学降解偶氮染料，不仅可以使废水达到很高的降解效率，而且可以大大降低能耗。
2.铁基非晶合金条带在降解染料废水时稳定性好、适用范围广。
3.铁基非晶合金的成分均匀性大大降低了铁的腐蚀速率，参加降解染料废水后的条带仍可保持非晶结构，且电极质量损失小，为其回收再重复利用提供了保障，延长了电极的使用寿命。
4.本发明涉及的铁基非晶合金来源广。随着非晶变压器的广泛应用，铁基非晶合金条带已有且将会有更多的废料，这包括在甩带、变压器加工过程中产生的次品以及变压器达到受用寿命后产生的废品等等。而将这些废弃的条带应用于染料废水的电化学降解可以达到以废治废的效益。不仅价格便宜，而且能实现对废弃能源整合利用。
5.本发明提供的电化学降解染料废水工艺操作简单，生产成本低，具备非常好的应用前景。
附图说明
图1为降解酸性橙II溶液反应前后的铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的XRD图谱。
图2为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的电化学降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线，以及Ct/C0随反应时间的变化曲线。其中电极电压为0.5V，溶液温度为60℃。
图3为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的电化学降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线，以及Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图4为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线，以及Ct/C0随反应时间的变化曲线。其中电极电压为0V，溶液温度为60℃。
图5为在铁基非晶合金条带Fe78Si8B14(at.％)的降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线，以及Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图6为在铁基非晶合金条带Fe83Si4B10P2Cu1(at.％)的电化学降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线，以及Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图7为在铁基非晶合金条带Fe65Co13Si8B14(at.％)的电化学降解作用下，酸性橙II溶液的Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图8为在铁基非晶合金条带Fe40Co38Si8B14(at.％)的电化学降解作用下，酸性橙II溶液的Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图9为在铁基非晶合金条带Fe68Ni10Si8B14(at.％)的电化学降解作用下，酸性橙II溶液的Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为 60℃。
图10为在铁基非晶合金条带Fe50Ni28Si8B14(at.％)的电化学降解作用下，酸性橙II溶液的Ct/C0随反应时间的变化曲线。其中电极电压为1V，溶液温度为60℃。
图11为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的降解作用下，电极电压分别为1V和0V时酸性橙II溶液反应前后的取样照片。
具体实施方式
以下结合附图及实施例详述本发明。
本发明利用甩带法得到铁基非晶合金条带，主要集中在Fe-B，Fe-Si-B，Fe-Co-Si-B，Fe-Ni-Si-B，Fe-Si-B-P，Fe-Si-B-Mo，Fe-Si-B-Nb，Fe-Si-B-P-Cu，Fe-Si-B-Nb-Cu，Fe-B-C，Fe-B-C-Nb，Fe-B-C-Cu，Fe-P-C Fe-P-C-Cu等合金体系，典型名义成分(原子百分比)如：Fe83B17，Fe78Si8B14，Fe65Co13Si8B14，Fe40Co38Si8B14，Fe68Ni10Si8B14，Fe50Ni28Si8B14，Fe83B10Si4P3，Fe77Si8B14Mo1，Fe74.5Nb3Si13.5B9，Fe83Si4B10P2Cu1，Fe73.5Nb3Cu1Si13.5B9，Fe84B10C6，Fe83Nb1B10C6，Fe83.5Cu0.5B10C6，Fe84P10C6，Fe83.25P10C6Cu0.75等，并应用于染料废水的电化学降解试验，试验结果表明，铁基非晶合金条带作为电极在电化学降解染料废水的过程中具有很好的稳定性，降解效率高的同时大大降低了电能耗。
图1为反应前后的铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的XRD图谱，反应前后条带的XRD图谱无明显差别，弥散峰说明了样品的非晶态结构。
将铁基非晶合金条带作为电极应用于电化学降解酸性橙II溶液，参与反应的电极表面积为50cm2，酸性橙II溶液浓度为0.2g/L，溶液体积为300mL。将盛有酸性橙II溶液的烧杯放置于电磁搅拌系统中以200rpm的转速对染料溶液进行搅拌，温度控制在60℃。选取电极电压分别为0.5V和1V进行试验。反应 开始后每间隔一定时间取出约3mL溶液进行紫外-可见光吸收光谱检测。根据光谱学知识，酸性橙II溶液的最大吸收峰为484nm，代表其偶氮结构(-N＝N-)，对应的吸光度与溶液溶度成正比，因此可以通过最大吸收峰处的吸光度变化得出溶液溶度变化。选取电极开路状态时进行对比试验，另外，在电极电压为0.5V时，选取高纯铁箔作为电极进行对比试验。
图2为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的电化学降解作用下，酸性橙II溶液的紫外-可见光吸收光谱随反应时间的变化曲线。如图2a所示，电极电压为0.5V，随着反应时间的增加，484nm处吸光度逐渐降低，意味着偶氮键(-N＝N-)不断断裂，酸性橙II不断被降解。图2b为酸性橙II降解的动力学曲线，进行非线性拟合后发现，降解过程满足假一级反应：
Ct/C0＝(1-Cult/C0)exp(-kt)+Cult/C0
其中，Ct和C0分别为t时刻和初始时刻的溶液浓度，Cult为溶液最终残余浓度，t为反应时间，k为反应速率常数，降解效率η＝1-Cult/C0。
电极电压为0.5V，反应240min时，酸性橙II溶液的降解效率可以达到90.42％，拟合得到的速率常数为0.014min-1。经过计算得到的电能耗为40.76J，单位降解效率的电能耗为0.45J/％，电极的质量损失为16mg。而用高纯铁箔作为电极时，在其他实验条件均相同的情况下，反应120min时，酸性橙II溶液的降解效率可以达到98.06％，电能耗为91.65J，单位降解效率的电能耗为0.94J/％，电极的质量损失为60mg。实验中高纯铁箔与铁基非晶合金条带具有相同的表面积，铁箔的厚度(100μm)是铁基非晶合金条带厚度(30μm)的三倍之多，而且，铁基非晶合金中含有大量非金属元素，因此，铁基非晶合金条带中单位表面积的铁含量远远少于高纯铁箔，然而铁基非晶合金条带作为电极时酸性橙II降解效率也能达到90％以上，可以说单位铁含量的铁基非晶合金条带作 为电极对酸性橙II溶液的降解效率肯定要大于高纯铁箔。而且，高纯铁箔作为电极时的能耗和电极质量损失远超出铁基非晶合金条带，由此可见，相对于高纯铁箔，铁基非晶合金条带作为电极电化学降解酸性橙II溶液时具有降解效率高、电极损耗少、电极寿命长、电能耗低等优点。
图3所示为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的电化学降解作用下，电极电压增加至1V时，酸性橙II溶液的降解过程，反应时间为30min时，降解效率即可达到92.67％，60min时可达到96.60％。可见电极电压一定幅度地升高有助于酸性橙II的降解。
图4为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)电极处于开路状态时，酸性橙II溶液的降解情况。可以看出，在没有电化学的作用下，铁基非晶合金条带对于酸性橙II的降解非常缓慢，反应300min时，降解效率仅仅为25.34％，反应速率常数为0.006min-1。可见，在电化学作用下，铁基非晶合金条带降解酸性橙II溶液的反应速率和降解效率均远远大于不加电的情况。
图5为在铁基非晶合金条带Fe78Si8B14(at.％)的电化学降解作用下，电极电压为1V时，酸性橙II溶液的降解过程。反应时间为10min时，降解效率即可达到95.47％，反应20min时，降解效率可达98.46％。由此可见，随着铁基非晶合金中Fe元素含量的提高，酸性橙II的降解速率加快。
以下实施例中参与反应的电极表面积为5cm2，酸性橙II溶液的体积为300mL，其他条件不变。图6为在铁基非晶合金条带Fe83Si4B10P2Cu1(at.％)的电化学降解作用下，酸性橙II溶液的降解过程。反应18min时，降解效率达97.32％，反应速率常数为0.295min-1。
图7为铁基非晶合金条带Fe65Co13Si8B14(at.％)电化学降解酸性橙II溶液，反应20min时，降解效率达96.19％，反应速率常数为0.225min-1。图8为铁基 非晶合金条带Fe40Co38Si8B14(at.％)电化学降解酸性橙II溶液，反应14min时，降解效率达97.94％，反应速率常数为0.435min-1。可见Fe基非晶合金中Co元素的少量添加并未显著影响降解效果，而Co元素含量增加则加快了铁基非晶合金条带电化学降解溶液的速率。
与Co元素类似，Fe基非晶合金中Ni元素的少量添加对降解也没有显著影响，而随着Ni元素含量的升高，铁基非晶合金条带电化学降解酸性橙II溶液的速率加快，如图9和10所示。图9为铁基非晶合金条带Fe68Ni10Si8B14(at.％)电化学降解酸性橙II，反应20min时，降解效率达96.19％，反应速率常数为0.217min-1。图10为铁基非晶合金条带Fe50Ni28Si8B14(at.％)电化学降解酸性橙II，反应20min时，降解效率达95.67％，反应速率常数为0.327min-1。
图11为在铁基非晶合金条带Fe73.5Nb3Cu1Si13.5B9(at.％)的降解作用下，电极电压分别为1V和0V时酸性橙II溶液反应前后的取样照片，可以看出在电化学作用下，反应60min，溶液即由初始的橙红色变为无色透明状态，而没有电化学作用时，反应300min，溶液颜色几乎没有明显变化。
为了进一步阐述本发明的技术先进性，补充以下比较例：
比较例1：
技术方案与实施例基本相同，铁基非晶合金成分为Fe78Si8B14(at.％)，不同之处为本比较例不加电流和电压，其余技术细节与实施例相同。试验结果表明，需经120min，才能有效降解偶氮染料，脱色效率为96.09％。显然，经过比较，可以发现，本发明技术方案的脱色效果得到了大大增强。
比较例2：
利用高纯铁箔和Fe78Si8B14铁基非晶合金作为电极时，电压为0.5V，其他实 验条件均相同。反应120min时，高纯铁箔作为电极时，酸性橙II溶液的降解效率可以达到98.06％，电能耗为91.65J，单位降解效率的电能耗为0.94J/％，电极的质量损失为60mg；而Fe78Si8B14铁基非晶合金作为电极时，酸性橙II溶液的降解效率可以达到98.35％，单位降解效率的电能耗为0.66J/％，电极的质量损失为21mg。由此可见，相对于高纯铁箔，铁基非晶合金条带作为电极电化学降解酸性橙II溶液时具有降解效率高、电极损耗少、电极寿命长、电能耗低等优点。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种工业废水处理用铁基非晶电极材料，其特征在于：所述材料为铁基非晶合金，作为电极用于电化学降解工业废水，该合金成分中铁元素的原子百分比在40～84％。
  2. 按照权利要求1所述染料废水处理用铁基非晶电极材料，其特征在于：所述铁基非晶合金中铁元素的原子百分比为65～84％，其他合金元素选自Si、B、P、C、Mo、Nb、Cu、Ni、Co中一种或几种。
  3. 按照权利要求1所述染料废水处理用铁基非晶电极材料，其特征在于：所述铁基非晶合金中铁元素的原子百分比为70～84％，其他合金元素选自Si、B、P、C、Mo、Nb、Cu、Ni、Co中一种或几种。
  4. 一种采用权利要求1～3任一所述铁基非晶电极材料处理染料废水的方法，其特征在于：采用铁基非晶合金条带作为电极应用于电化学降解工业废水，其电极电位为0～5V。
  5. 按照权利要求4所述铁基非晶电极材料处理工业废水的方法，其特征在于：铁基非晶合金条带作为电极，流过其的电流为0.005A～1A。
  6. 按照权利要求4所述铁基非晶电极材料处理工业废水的方法，其特征在于：采用的铁基非晶合金条带通过甩带法制备，条带厚度为15μm～100μm。
  7. 按照权利要求4所述铁基非晶电极材料处理染料废水的方法，其特征在于：染料废水溶液的浓度为20mg/L～2000mg/L，溶液的温度为环境温度到100℃，溶液的pH值为1～12。
  8. 按照权利要求4所述铁基非晶电极材料处理染料废水的方法，其特征在于：染料废水溶液中铁基非晶合金条带的比表面积浓度大于100cm2/(g·L)。
  9. 一种权利要求1所述铁基非晶电极材料在电化学降解工业废水方面的应用。
  10. 按照权利要求9所述铁基非晶电极材料在电化学降解工业废水方面的应用，其特征在于：所述工业废水为染料废水。
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