CN110713242A - Zero-valent iron material Fe @ iron fluoride and preparation method thereof - Google Patents
Zero-valent iron material Fe @ iron fluoride and preparation method thereof Download PDFInfo
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- CN110713242A CN110713242A CN201910734584.8A CN201910734584A CN110713242A CN 110713242 A CN110713242 A CN 110713242A CN 201910734584 A CN201910734584 A CN 201910734584A CN 110713242 A CN110713242 A CN 110713242A
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention relates to a zero-valent iron material Fe @ iron fluoride and a preparation method thereof. The invention provides a zero-valent iron material Fe @ iron fluoride, wherein the surface layer of the zero-valent iron material is an iron fluoride layer, and the iron fluoride layer replaces iron oxide of a zero-valent iron shell layer. The preparation method comprises the following steps: and heating and reacting the hydrofluoric acid solution with zero-valent iron for a period of time, and performing post-treatment to obtain the zero-valent iron material Fe @ iron fluoride. The zero-valent iron material Fe @ iron fluoride provided by the invention has extremely high activity, can greatly promote the corrosion efficiency of zero-valent iron, improves the heavy metal removal efficiency and the utilization rate of the zero-valent iron, and is beneficial to saving the cost of the zero-valent iron technology.
Description
Technical Field
The invention belongs to the field of pollutant remediation in water and preparation of environmental materials, and particularly relates to a novel zero-valent iron material Fe @ iron fluoride, a preparation method and application thereof in pollutant removal.
Background
The zero-valent iron is used as a green, environment-friendly, economic and efficient multifunctional environment-friendly material and has good research and application prospects. Through research and development for more than 20 years, zero-valent iron has a good effect in the aspects of treating heavy metals, organic matters, nitrogen, phosphorus, mixed pollutants and the like, but the large-area application of the zero-valent iron in actual environmental remediation still has a challenge, mainly because iron is easy to react with oxygen or water, an iron oxide shell layer is formed on the surface of the zero-valent iron, and the iron oxide shell layer plays a role in protecting the zero-valent iron from being further oxidized and simultaneously can prevent the zero-valent iron from being corroded, namely the capacities of the iron to give electrons and release divalent iron ions are influenced. In order to solve this problem, researchers of the zero-valent iron technology have proposed various modification technologies, such as synthesis of nano zero-valent iron by changing the particle size of zero-valent iron, preparation of bimetallic materials such as iron copper or iron nickel, pretreatment of hydrogen and hydrochloric acid, reinforcement of weak magnetic field and microwave and electric field, and reinforcement technology of adding inorganic ions. Although the above improved technology can effectively improve the pollutant removal capability of zero-valent iron, researchers find that a new iron oxide shell layer is formed on the surface of zero-valent iron as the reaction proceeds, so that the utilization efficiency of zero-valent iron is affected, and therefore how to further improve the utilization efficiency of zero-valent iron is an urgent problem to be solved for influencing the comprehensive popularization and application of the zero-valent iron technology.
Disclosure of Invention
The invention aims to provide a novel zero-valent iron material Fe @ iron fluoride and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the zero-valent iron material Fe @ iron fluoride is provided, the surface layer of the zero-valent iron material is an iron fluoride layer, and the iron fluoride layer replaces the iron oxide of the zero-valent iron shell layer.
In the above scheme, the iron fluoride includes but is not limited to Fe3F8·2H2O and Fe2F5·2H2O。
The preparation method of the zero-valent iron material Fe @ iron fluoride is provided, wherein hydrofluoric acid solution and zero-valent iron are heated and reacted for a period of time, and the zero-valent iron material Fe @ iron fluoride is obtained through post-treatment.
According to the scheme, the post-treatment comprises the following steps: after solid-liquid separation, washing with deionized water and ethanol respectively, and finally drying in a vacuum drying oven. The solid-liquid separation process can adopt the technologies of magnetic separation, gravity separation, centrifugal separation and the like.
According to the scheme, the mixture is washed for 3 times by deionized water and ethanol respectively, and dried for 12-18h in a vacuum drying oven at 25 ℃.
According to the scheme, the hydrofluoric acid is sourced from hydrofluoric acid wastewater discharged by industries such as market or photovoltaics.
According to the scheme, the concentration of the hydrofluoric acid is 0.1-2M, and the dosage of the zero-valent iron is 80-400 g/L.
According to the scheme, the reaction temperature is 50-120 ℃, and the reaction time is 2-7 h.
According to the scheme, the zero-valent iron is micron-sized zero-valent iron.
Provides a method for removing heavy metal pollution by using the zero-valent iron material Fe @ iron fluoride.
According to the scheme, the addition amount of the zero-valent iron material Fe @ iron fluoride is 0.2-1 g/L.
According to the scheme, the heavy metal pollution comprises chromium and arsenic.
According to the scheme, the heavy metal pollution concentration is 1-10 mg/L.
According to the scheme, stirring is carried out in the removing process, and the rotating speed can be 200 r/min.
The invention has the beneficial effects that:
the invention takes zero-valent iron (such as factory scrap iron, commercial zero-valent iron powder and the like) as a raw material, adds hydrofluoric acid for heating and modification, destroys the original iron oxide shell layer of the zero-valent iron by utilizing the acidity of hydrofluoric acid, and further forms a new iron fluoride layer on the surface of the zero-valent iron, so that the hydrophilicity of the prepared Fe @ iron fluoride is greatly improved, the Fe @ iron fluoride has extremely high activity, the corrosion efficiency of the zero-valent iron is greatly promoted, the efficiency of removing heavy metal and the utilization rate of the zero-valent iron are improved, and the cost of the zero-valent iron technology is saved.
Drawings
FIG. 1 is an XRD results plot of the original zero-valent iron (B) and Fe @ iron fluoride (Fe @ iron fluoride) (A) (example 1) (. t.Fe)3F8·2H2O(PDF 76-2285)◆Fe2F5·2H2O(PDF 84-0880)▲Fe0)；
FIG. 2 shows the original zero-valent iron (A) and Fe @ iron fluoride (Fe @ FeF)x) Graph of contact angle results of (B) (example 1);
FIG. 3 shows Fe @ iron fluoride (Fe @ FeF)x) Removal of chromium heavy metalsFruit (example 1);
FIG. 4 shows Fe @ Fe fluoride (Fe @ FeF)x) Removal of heavy metal arsenic (example 1).
Detailed Description
Example 1
Firstly, 50mL of 0.1M hydrofluoric acid solution is prepared and put into a 100mL polytetrafluoroethylene bottle, and 4g of zero-valent iron is added. Reacting for 3h at 50 ℃, washing for 3 times by using deionized water and ethanol respectively, and filtering and drying a sample for 18h at 25 ℃ in a vacuum drying oven to obtain Fe @ iron fluoride. XRD results for the original zero-valent iron (a) and Fe @ iron fluoride (B), fig. 1 illustrates: the ferric fluoride layer ferric fluoride/ferrous mineral shell replaces the ferric oxide layer of the zero-valent iron shell. The contact angle results of the original zero-valent iron (A) and Fe @ iron fluoride (B) are shown in FIG. 2, and FIG. 2 illustrates that the hydrophilicity of the zero-valent iron material Fe @ iron fluoride is greatly improved.
At the rotation speed of 200 r/min, the initial concentration of hexavalent chromium is 5mg/L, the initial concentration of pentavalent arsenic is 1mg/L, the dosage of Fe @ iron fluoride is 0.2g/L, after the reaction is carried out for 30min, the removal rate of chromium reaches 90%, the removal rate of arsenic reaches 90%, and the removal efficiency of original zero-valent iron chromium and arsenic is about 3% and 15%. The utilization rate of zero-valent iron of the modified zero-valent iron Fe @ iron fluoride material reaches 50%, and the utilization rate of original zero-valent iron is only 10% (the utilization rate of zero-valent iron is the proportion of the amount of zero-valent iron consumed in the reaction to the total zero-valent iron, and can be characterized and quantified through XRD). The results of chromium and arsenic removal are shown in fig. 3 and 4, respectively.
Example 2
Firstly, 50mL of 1M hydrofluoric acid solution is prepared and put into a 100mL polytetrafluoroethylene bottle, and 6g of zero-valent iron is added. Reacting for 2h at 75 ℃, then washing for 3 times by using deionized water and ethanol respectively, filtering a sample, and drying for 12h at 25 ℃ in a vacuum drying oven to obtain Fe @ iron fluoride;
the rotating speed is 200 r/min, the initial concentration of hexavalent chromium is 10mg/L, the initial concentration of pentavalent arsenic is 2mg/L, the adding amount of Fe @ iron fluoride is 0.2g/L, after the reaction is carried out for 30min, the removal rate of chromium reaches 91%, and the removal rate of arsenic reaches 90%.
Example 3
Firstly, 50mL of 2M hydrofluoric acid solution is prepared and put into a 100mL polytetrafluoroethylene bottle, and 10g of zero-valent iron is added. Reacting for 2h at 75 ℃, then washing for 3 times by using deionized water and ethanol respectively, and filtering and drying a sample for 18h at 25 ℃ in a vacuum drying oven;
the rotating speed is 200 r/min, the initial concentration of hexavalent chromium is 5mg/L, the initial concentration of pentavalent arsenic is 1mg/L, the adding amount of Fe @ iron fluoride is 0.2g/L, after the reaction is carried out for 30min, the removal rate of chromium reaches 98%, and the removal rate of arsenic reaches 93%.
Example 4
Firstly, 50mL of 2M hydrofluoric acid solution is prepared and put into a 100mL polytetrafluoroethylene bottle, and 16g of zero-valent iron is added. Reacting for 2h at 120 ℃, then washing for 3 times by using deionized water and ethanol respectively, and filtering and drying a sample for 18h at 25 ℃ in a vacuum drying oven;
the rotating speed is 200 r/min, the initial concentration of hexavalent chromium is 5mg/L, the initial concentration of pentavalent arsenic is 1mg/L, the adding amount of Fe @ iron fluoride is 0.2g/L, after the reaction is carried out for 30min, the removal rate of chromium reaches 99%, and the removal rate of arsenic reaches 95%.
The zero-valent iron of the above embodiment is micron-sized zero-valent iron, the particle size is greater than 5 microns, and the source is: factory scrap iron, commercial zero-valent iron powder and the like.
Claims (10)
1. A zero-valent iron material Fe @ iron fluoride is characterized in that: the surface layer of the zero-valent iron material is an iron fluoride layer, and the iron fluoride layer replaces the iron oxide of the zero-valent iron shell layer.
2. The zero-valent iron material Fe @ iron fluoride of claim 1, wherein: the iron fluoride includes but is not limited to Fe3F8·2H2O and Fe2F5·2H2O。
3. A method of preparing the zero-valent iron material Fe @ iron fluoride of claim 1, wherein: the method comprises the following steps: and heating and reacting the hydrofluoric acid solution with zero-valent iron for a period of time, and performing post-treatment to obtain the zero-valent iron material Fe @ iron fluoride.
4. The method of claim 3, wherein: the post-treatment comprises the following steps: after solid-liquid separation, washing with deionized water and ethanol respectively, and finally drying in a vacuum drying oven.
5. The method of claim 3, wherein: the zero-valent iron is micron-sized zero-valent iron; the hydrofluoric acid is from hydrofluoric acid wastewater discharged by industries such as market or photovoltaic industry.
6. The method according to claim 3, wherein the hydrofluoric acid concentration is 0.1-2M and the amount of zero-valent iron is 80-400 g/L.
7. The process according to claim 3, wherein the reaction temperature is 50 to 120 ℃ and the reaction time is 2 to 7 hours.
8. A method of removing heavy metal contamination using the zero-valent iron material Fe @ iron fluoride of claim 1.
9. The method of claim 8, wherein: the dosage of the zero-valent iron material Fe @ iron fluoride is 0.2-1 g/L.
10. The method of claim 8, wherein: said heavy metal contamination comprises chromium and arsenic; the heavy metal pollution concentration is 1-10 mg/L; stirring is carried out in the removing process.
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| CN110606536A (en) * | 2019-08-02 | 2019-12-24 | 华中师范大学 | Method for synchronously removing phosphorus and preparing phosphorylated zero-valent iron and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826616A (en) * | 2012-09-13 | 2012-12-19 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| US20150129507A1 (en) * | 2013-11-11 | 2015-05-14 | Peroxychem Llc | Treatment of arsenic contaminated soil and water |
| CN106025182A (en) * | 2016-08-03 | 2016-10-12 | 广东工业大学 | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof |
| CN106732691A (en) * | 2017-01-20 | 2017-05-31 | 四川师范大学 | A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof |
| CN108404942A (en) * | 2018-02-02 | 2018-08-17 | 武汉工程大学 | A kind of fluorine richness Fe3O4Magnetic Nano material and its preparation method and application |
| CN108911101A (en) * | 2018-06-25 | 2018-11-30 | 华中师范大学 | A method of based on the efficient heavy-metal ion removal of ball milling oxalic acid Zero-valent Iron |
| CN109110901A (en) * | 2018-09-03 | 2019-01-01 | 华中师范大学 | The method for efficiently removing heavy metal contaminants based on fluorination Zero-valent Iron |
| CN109205754A (en) * | 2018-09-11 | 2019-01-15 | 华中师范大学 | A kind of method that phosphatization promotes nano zero valence iron reduction heavy-metal ion removal |
| CN109384299A (en) * | 2018-08-10 | 2019-02-26 | 华中师范大学 | A kind of method that the modified Zero-valent Iron of sodium oxalate removes Cr VI in water body |
-
2019
- 2019-08-09 CN CN201910734584.8A patent/CN110713242B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826616A (en) * | 2012-09-13 | 2012-12-19 | 广东电网公司电力科学研究院 | Ferric fluoride nano material and preparation method thereof |
| US20150129507A1 (en) * | 2013-11-11 | 2015-05-14 | Peroxychem Llc | Treatment of arsenic contaminated soil and water |
| CN106025182A (en) * | 2016-08-03 | 2016-10-12 | 广东工业大学 | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof |
| CN106732691A (en) * | 2017-01-20 | 2017-05-31 | 四川师范大学 | A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof |
| CN108404942A (en) * | 2018-02-02 | 2018-08-17 | 武汉工程大学 | A kind of fluorine richness Fe3O4Magnetic Nano material and its preparation method and application |
| CN108911101A (en) * | 2018-06-25 | 2018-11-30 | 华中师范大学 | A method of based on the efficient heavy-metal ion removal of ball milling oxalic acid Zero-valent Iron |
| CN109384299A (en) * | 2018-08-10 | 2019-02-26 | 华中师范大学 | A kind of method that the modified Zero-valent Iron of sodium oxalate removes Cr VI in water body |
| CN109110901A (en) * | 2018-09-03 | 2019-01-01 | 华中师范大学 | The method for efficiently removing heavy metal contaminants based on fluorination Zero-valent Iron |
| CN109205754A (en) * | 2018-09-11 | 2019-01-15 | 华中师范大学 | A kind of method that phosphatization promotes nano zero valence iron reduction heavy-metal ion removal |
Non-Patent Citations (1)
| Title |
|---|
| 山西省电力工业局: "《化学设备运行技术》", 31 July 1985, 水利电力出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606536A (en) * | 2019-08-02 | 2019-12-24 | 华中师范大学 | Method for synchronously removing phosphorus and preparing phosphorylated zero-valent iron and application thereof |
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