WO2016024774A1 - Structure de fer pour le traitement des eaux usées par oxydation fenton, son procédé de préparation et procédé de traitement des eaux usées faisant appel à ladite structure - Google Patents

Structure de fer pour le traitement des eaux usées par oxydation fenton, son procédé de préparation et procédé de traitement des eaux usées faisant appel à ladite structure Download PDF

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Publication number
WO2016024774A1
WO2016024774A1 PCT/KR2015/008350 KR2015008350W WO2016024774A1 WO 2016024774 A1 WO2016024774 A1 WO 2016024774A1 KR 2015008350 W KR2015008350 W KR 2015008350W WO 2016024774 A1 WO2016024774 A1 WO 2016024774A1
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Prior art keywords
iron
oxidation treatment
fenton oxidation
wastewater
plate
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PCT/KR2015/008350
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English (en)
Korean (ko)
Inventor
박재우
장준원
김혜란
김슬기
정종진
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한양대학교 산학협력단
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Publication of WO2016024774A1 publication Critical patent/WO2016024774A1/fr

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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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation

Definitions

  • the present invention relates to a novel iron structure for fenton oxidation treatment of wastewater, a method for producing the same, and a wastewater treatment method using the same.
  • chemical treatment techniques generally include oxidation methods such as ozone, hydrogen peroxide, UV / O 3 , UV / TiO 2 , and fenton, among which fenton does not form chlorides and both iron and hydrogen peroxide have relatively low toxicity.
  • oxidation methods such as ozone, hydrogen peroxide, UV / O 3 , UV / TiO 2 , and fenton, among which fenton does not form chlorides and both iron and hydrogen peroxide have relatively low toxicity.
  • the process injects Fe 2+ form iron salt into raw water to accelerate the generation of hydrogen peroxide and OH into raw water, and rapidly oxidizes and removes organic substances in the water. It is widely used.
  • the problem to be solved by the present invention is to provide a novel wastewater fenton oxidation treatment iron structure and its manufacturing method to solve the conventional problems and at the same time have an excellent Fenton reaction efficiency, and to provide a wastewater treatment method using the same do.
  • the present invention provides an iron structure for fenton oxidation treatment of wastewater formed by anodizing, in order to solve the above problems, the iron structure according to the present invention is a ferric oxide (Fe) oxide on the surface of the plate (plate) made of iron (Fe 0 ) It is characterized in that the nanostructure of Fe 2 O 3 ) is formed.
  • Fe ferric oxide
  • ferric oxide nano structure is characterized in that it has a nano-leaf (Nano-leaf) shape.
  • the 'nano-leaf' is a shape having a leaf shape such as an irregular wire having a grphen-like shape or a face shape (the aspect ratio is close to 1) similar to graphene. It can be confirmed, more specifically in Figures 3a and 3b below.
  • the surface of the nanostructure is characterized in that the nanostructure of ferric oxide is hematite, and the plate is ferrous iron (Fe 0 ).
  • the present invention provides a method for producing an iron structure for fenton oxidation treatment of wastewater comprising the following steps.
  • step (b) continuing the anodic oxidation step of step (a) to oxidize the non-ferrous iron surface;
  • power may be applied at a voltage of 10-15 V in step (a), preferably 12 V voltage.
  • the surface of the anodized plate in step (b) is characterized in that the ferrous oxide (FeO) of the wustite crystal structure (FeO), the surface of the plate annealed in the step (c) is hematite (hematite) Ferric oxide (Fe 2 O 3 ) having a crystal structure.
  • the ferrous oxide (FeO) of the wustite crystal structure (FeO) the surface of the plate annealed in the step (c) is hematite (hematite) Ferric oxide (Fe 2 O 3 ) having a crystal structure.
  • the present invention provides a wastewater treatment method comprising the following steps using the iron structure for fenton oxidation treatment according to the present invention.
  • the pseudo-fentone reaction occurs in the surface nanostructure of the iron structure for fenton oxidation treatment, it is characterized in that the oxidation of the organic material contained in the wastewater.
  • the electron is continuously supplied to the surface from the plate of the iron structure for fenton oxidation treatment.
  • the iron structure for the fenton oxidation catalyst according to the present invention has a nano structure formed on the surface thereof, so that the surface area is improved, the fenton oxidation treatment efficiency is excellent, and electrons are continuously supplied to the surface to enable semi-permanent use.
  • the nanostructures are fixed to the plate, there is an advantage of easy operation of the catalyst. In addition, it can be performed even in an alkaline state of about pH 12, there is no generation of iron sludge and economical environmental treatment process can be implemented.
  • Figure 1 is a cross-sectional view of the iron structure for fenton oxidation treatment according to the present invention, a cross-sectional view showing a nanostructure of ferric oxide formed on a plate of a non-ferrous iron and its surface, SEM image is an image showing a surface nanoleaf structure.
  • FIG. 2 is a graph showing a current change curve with time during anodization according to an embodiment of the present invention.
  • 3A and 3B are scanning microscope images showing top-view and bottom-view of the iron oxide nanostructures formed on the iron plate surface according to Example 1, respectively.
  • Figure 4 is an XRD graph analyzed through Crystal Impact Match for the iron structure formed on the surface of the iron plate produced according to the present invention.
  • Figures 5a and 5b is an external appearance image of the iron structure after the annealing process and the external appearance image of the iron structure produced by the anodizing process of Example 1 according to the present invention, respectively.
  • 6A to 6C are graphs showing the results of Fenton experiments performed using hydrogen peroxide and commercial iron catalyst powder using hydrogen peroxide, respectively, using hydrogen peroxide and the iron structure for fenton oxidation treatment according to the present invention.
  • FIG. 7 is a graph showing ammonia nitrogen removal efficiency according to the amount of zeolite according to an embodiment of the present invention.
  • FIG 8 is an image showing the result of the before and after the final treatment water treatment of livestock wastewater according to an embodiment of the present invention.
  • FIG. 9 is a schematic diagram of an anodization process apparatus schematically showing an anodization process according to the present invention.
  • the present invention is to provide an iron structure for the Fenton oxidation catalyst having a new structure to solve the low economic efficiency compared to the efficiency.
  • the iron structure for the fenton oxidation catalyst according to the present invention is an immobilized fenton reaction in the form of a plate, characterized in that the control of the catalyst is easy and can be reused.
  • the nanostructure of ferric oxide (Fe 2 O 3 ) is formed on the surface of the plate (plate) made of ductile iron (Fe 0 ) It is characterized by being.
  • This novel structure can be produced by forming a nanostructure of ferric oxide (Fe 2 O 3 ) on the surface through an anodization process and an annealing process using an iron plate as an anode.
  • Fe 2 O 3 ferric oxide
  • the quasi-Fenton reaction with hydrogen peroxide is carried out, characterized in that the organic pollutants in the wastewater can be treated by OH radicals.
  • the quasi-Fenton reaction is continuously performed by continuously supplying electrons to the nanostructure of the surface in the plate made of ductile iron.
  • the iron structure for fenton oxidation treatment according to the present invention to form a nano-structured structure having a high surface area on the surface of the iron catalyst to efficiently perform the Fenton reaction on the plate of iron iron to fix the iron catalyst to react It is called Immobilized Fenton Reaction, which is easy to control.
  • the nanostructure of the ferric oxide has a nano-leaf (Nano-leaf) shape
  • the nano-leaf (Nano-leaf) shape is graphene-like form (grphen-like) or surface shape (aspect ratio of 1 Close to the shape of the shape having a leaf shape such as an irregular wire (wire), and more specifically, it can be confirmed in FIGS. 3A and 3B below.
  • the surface is hematite of ferric oxide (hematite)
  • the plate is characterized in that the ferric iron (Fe 0 ).
  • Another aspect of the invention relates to a method for producing an iron structure for fenton oxidation treatment of wastewater comprising the following steps.
  • step (b) continuing the anodic oxidation step of step (a) to oxidize the non-ferrous iron surface;
  • power may be applied at a voltage of 10-15 V in step (a), preferably 12 V voltage.
  • the reaction time may be 2-5 hours, when the reaction time is out of the range, there is a problem in the production of nanocrystalline form in the process of forming the ferric oxide (FeO) crystal form by anodization There may be a problem that the amorphous form is generated and the Fenton processing efficiency is lowered.
  • the surface of the anodized plate in step (b) is characterized in that the ferrous oxide (FeO) of the wustite crystal structure (FeO), the surface of the plate annealed in the step (c) is hematite (hematite) Ferric oxide (Fe 2 O 3 ) having a crystal structure.
  • the ferrous oxide (FeO) of the wustite crystal structure (FeO) the surface of the plate annealed in the step (c) is hematite (hematite) Ferric oxide (Fe 2 O 3 ) having a crystal structure.
  • Another aspect of the present invention relates to a wastewater treatment method comprising the following steps using the iron structure for fenton oxidation treatment according to the present invention.
  • the pseudo-fentone reaction occurs in the surface nanostructure of the iron structure for fenton oxidation treatment, it is characterized in that the oxidation of the organic material contained in the wastewater.
  • the electron is continuously supplied to the surface from the plate of the iron structure for fenton oxidation treatment.
  • Wastewater treatment method is to be carried out in the neutral state and pH 12 alkali conditions, and the iron sludge, the process was carried out at low conditions of pH 3-5, which is a problem in the conventional Fenton process It is possible to use semi-permanent use of iron catalyst and economical environmental treatment process is possible.
  • the iron used in the present invention was 99.0% in purity, and an iron plate cut to a size of 40 mm to 100 mm was used to favor anodization and electroreduction.
  • Chemical etching was performed to remove contaminants of the organic content on the iron plate surface, and hydrofluoric acid, nitric acid, and distilled water were mixed at a volume ratio of 1: 4: 5.
  • the iron plate sample was immersed in the prepared solution for about 30 seconds, then taken out, and ultrasonically cleaned for about 20 minutes with distilled water. At this time, the chemical etching was not performed for more than 1 minute because metal defects or toxic gases may be generated due to hydrogen embrittlement.
  • an electrolyte containing 0.25 wt% NaF in Na 2 SO 4 1 M was used as an anodizing solution.
  • anodization using EG electrolyte was carried out using a PNCYS EP1605 model, and anodization was performed by a constant voltage method with a fixed voltage of 12 V.
  • an iron plate was used as the positive electrode, and 95% platinum or copper was dissolved as the negative electrode, and the metal plates were equilibrated at 5-8 cm intervals.
  • the temperature was maintained at 5 ° C. through cooling water, and the anodization time was fixed at 3 hours, after which the mixture was washed with distilled water and methanol and dried at 60 ° C. in an oven.
  • Example 1 In the anodization process of Example 1 was carried out in the same manner except for adjusting the voltage to 4, 8, 16V instead of 12V.
  • the surface of the initial iron plate is changed to iron oxide in the form of nanostructure through anodization at 12V.
  • 3A and 3B are scanning microscope images showing a top-view and a bottom-view of an iron oxide structure formed on an iron plate surface according to Example 1, respectively, wherein the structure formed according to the present invention has a graphene-like shape (grphen- It is in the form of a nano laef with a leaf shape such as an irregular wire having a like or face shape (aspect ratio close to 1).
  • grphen- It is in the form of a nano laef with a leaf shape such as an irregular wire having a like or face shape (aspect ratio close to 1).
  • the crystal form of the iron structure formed on the surface of the iron plate produced according to the present invention was confirmed through an XRD graph, and analyzed through Crystal Impact Match. The results are shown in FIG. 4.
  • the initial iron plate is a ferrous iron (Fe 0 , raw iron), the surface is changed to wustite (FeO (ferrous oxide)) after the anodization process, and then annealing process After passing through the surface, hematite (hematite, Fe 2 O 3 (ferric oxide)) can be confirmed that the change.
  • FeO ferrous iron
  • hematite hematite, Fe 2 O 3 (ferric oxide)
  • FIG. 5a The exterior image of the iron structure manufactured by the anodization process of Example 1 is as shown in Figure 5a, after which the exterior image of the iron structure undergoes an annealing process is shown in Figure 5b.
  • the baseline was met after 360 minutes with commercial iron catalyst powder (0.9 g) with 882 mM hydrogen peroxide.
  • reaction time was shortened by half compared with the case of using the commercial iron catalyst powder of (2).
  • the sample was collected from the Hamyang Livestock Wastewater Treatment Plant, and after the precipitation and dehydration process, the experiment was carried out using the filtrate, and refrigerated after storage to minimize the change in appearance.
  • zeolite used in this experiment was purchased by using a zeolite manufactured by Wako, Japan, and the particle size of the zeolite has a size of 75 ⁇ m (200 mesh).
  • concentration of ammonium ions was analyzed by ion-selective electrode (ISE, Neonet Dual pH meter) method, and ionic strength adjuster (ISA) was used to remove other interferences and maintain ionic strength at a constant and high value.
  • the livestock wastewater was treated with Fenton using 1 g of iron catalyst for fenton oxidation according to the present invention (hydrogen peroxide was fixed at 3% in the previous experiment), and the total efficiency was 80% in 60 minutes. Hematite showed 70% treatment efficiency.
  • TOC since the oxidized amount of organic matter is measured, it is possible to perform a complete treatment if the efficiency is 70% or more, and the iron catalyst for fenton oxidation treatment according to the present invention shows much higher efficiency than general hematite treatment. appear.
  • ammonia nitrogen treatment efficiency was measured using zeolite in order to treat ammonia nitrogen. As a result, when 1 g of zeolite was used, the reaction efficiency was 90% at 45 minutes. When a larger amount of zeolite was added, ammonia nitrogen increased by desorption after 45 minutes.
  • FIG. 8 it is a photograph of the result of the last treatment before a livestock wastewater treatment and even ammonia nitrogen. After high turbidity was filtered to zeolite, it was confirmed that the result was a very transparent form.
  • the iron structure for the fenton oxidation catalyst and the wastewater treatment process using the same according to the present invention are not only excellent in fenton oxidation treatment efficiency, do not generate iron sludge, and can be used semi-permanently, which is useful for environmental treatment process industries such as wastewater treatment. Can be utilized.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne une structure de fer pour le traitement par oxydation Fenton, possédant une nouvelle structure, un oxyde ferrique nanostructuré dans lequel une réaction de type Fenton est réalisée sur la surface de celui-ci étant formé sur sa surface, et cette nanostructure étant fixée sur une plaque. La structure de fer destinée au traitement par oxydation Fenton possède une excellente efficacité de traitement par oxydation Fenton et peut être utilisée de façon semi-permanente. Elle s'avère donc utile dans l'industrie des processus de traitement environnemental comme le traitement des eaux usées.
PCT/KR2015/008350 2014-08-12 2015-08-10 Structure de fer pour le traitement des eaux usées par oxydation fenton, son procédé de préparation et procédé de traitement des eaux usées faisant appel à ladite structure WO2016024774A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105964308A (zh) * 2016-05-27 2016-09-28 东莞市联洲知识产权运营管理有限公司 一种污水处理用催化剂载体材料的制备方法
CN107640854A (zh) * 2017-09-25 2018-01-30 复旦大学 一种氧化时间以秒计的印染废水深度处理一体化方法
CN107899578A (zh) * 2017-10-25 2018-04-13 浙江科技学院 一种粽状微米级氧化铁非均相类光芬顿催化剂及其制备方法
CN110961107A (zh) * 2019-12-10 2020-04-07 重庆工商大学 一种纳米氧化铁材料、其制备方法及应用
CN112358900A (zh) * 2020-10-26 2021-02-12 沈阳工业大学 一种芬顿试剂氧化煤脱硫方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105964308A (zh) * 2016-05-27 2016-09-28 东莞市联洲知识产权运营管理有限公司 一种污水处理用催化剂载体材料的制备方法
CN107640854A (zh) * 2017-09-25 2018-01-30 复旦大学 一种氧化时间以秒计的印染废水深度处理一体化方法
CN107899578A (zh) * 2017-10-25 2018-04-13 浙江科技学院 一种粽状微米级氧化铁非均相类光芬顿催化剂及其制备方法
CN107899578B (zh) * 2017-10-25 2020-05-26 浙江科技学院 一种粽状微米级氧化铁非均相类光芬顿催化剂及其制备方法
CN110961107A (zh) * 2019-12-10 2020-04-07 重庆工商大学 一种纳米氧化铁材料、其制备方法及应用
CN110961107B (zh) * 2019-12-10 2023-03-28 重庆工商大学 一种纳米氧化铁材料、其制备方法及应用
CN112358900A (zh) * 2020-10-26 2021-02-12 沈阳工业大学 一种芬顿试剂氧化煤脱硫方法

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