CN112079417A - Surface humation zero-valent iron and preparation method and application thereof - Google Patents
Surface humation zero-valent iron and preparation method and application thereof Download PDFInfo
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- CN112079417A CN112079417A CN202011010874.7A CN202011010874A CN112079417A CN 112079417 A CN112079417 A CN 112079417A CN 202011010874 A CN202011010874 A CN 202011010874A CN 112079417 A CN112079417 A CN 112079417A
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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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
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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
- C02F2101/30—Organic 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
Surface humation-like zero-valent iron is obtained by the following method: respectively weighing sugar substances and zero-valent iron according to the mass ratio, then ball-milling by using a ball mill, converting the sugar substances into humoid substances and loading the humoid substances onto a zero-valent iron shell layer to prepare the surface humus-like zero-valent iron. The invention also discloses a preparation method of the surface humified zero-valent iron. The invention converts the saccharides into humoid to be modified to the zero-valent iron shell, changes the structure and chemical composition of the zero-valent iron shell and forms surface humus-like zero-valent iron. The surface humation zero-valent iron has high pollutant removal efficiency and transmission capacity, can be used for removing typical heavy metals and organic pollutants in water, and has the removal efficiency of more than 99%. The method has the advantages of simple operation, economy, high efficiency and environmental protection.
Description
Technical Field
The invention belongs to the field of preparation of contaminated site repairing materials, and particularly relates to surface humation-like zero-valent iron.
The invention also relates to a preparation method of the surface humation zero-valent iron.
The invention also relates to application of the surface humation zero-valent iron in removing pollutants in water.
Background
Compared with other site pollution remediation technologies, the zero-valent iron technology has the characteristics of rich sources, ecological environmental protection, economy, high efficiency, simplicity in operation and the like, and is widely concerned and applied in the field of site remediation. Through long-term application and development, the zero-valent iron technology has excellent effect on treating pollution of some actual sites, but the wide application of the zero-valent iron technology still has challenges. For example, micron-sized zero-valent iron has a problem of low activity, which is manifested by poor electron selectivity, slow corrosion of zero-valent iron, and the like.
The reasons for the above problems are: when the zero-valent iron is generated and used, a ferrite/hydroxide passivation layer is formed on the surface of the zero-valent iron, and the passivation layer can prevent the zero-valent iron from corroding and influence the removal of pollutants.
In order to solve the problems, researchers have developed various improvement strategies to improve the activity and the transmission capability of zero-valent iron. For example, the preparation of nano zero-valent iron, sulfuration and oxalation zero-valent iron, bimetallic materials and supported zero-valent iron, the application of weak magnetic field, acid washing, hydrogen pretreatment, ultrasonic treatment and other methods. Although the above strategies can improve the activity or the transmission capability of the zero-valent iron, the above zero-valent iron improvement technology has the problems of complicated operation, additional equipment requirement, potential secondary pollution or excessive cost and the like.
Disclosure of Invention
The invention aims to provide surface humation-like zero-valent iron.
Still another object of the present invention is to provide a method for producing the above surface-humified zero-valent iron.
In order to achieve the purpose, the surface humation zero-valent iron provided by the invention is obtained by the following method:
respectively weighing sugar substances and zero-valent iron according to the mass ratio, then ball-milling by using a ball mill, converting the sugar substances into humoid to be loaded on a zero-valent iron shell layer, and preparing the surface humus-like zero-valent iron.
The surface humation zero-valent iron is characterized in that the saccharide substances comprise monosaccharide, disaccharide and/or polysaccharide substances.
The surface humation-like zero-valent iron is characterized in that the mass ratio of the sugar substance to the zero-valent iron is 1:5-1: 50.
The invention provides a method for preparing the surface humation zero-valent iron, which comprises the following steps:
respectively weighing sugar substances and zero-valent iron according to the mass ratio, then ball-milling by using a ball mill, converting the sugar substances into humoid to be loaded on a zero-valent iron shell layer, and preparing the surface humus-like zero-valent iron.
The method of (a), wherein the saccharide substance comprises a monosaccharide, disaccharide and/or polysaccharide substance.
The surface humus-like zero-valent iron is characterized in that the saccharide substances comprise xylose, glucose and/or starch.
The method comprises the step of preparing the saccharides and the zero-valent iron according to the mass ratio of 1:5-1: 50.
The method comprises the steps that the ball milling time is 2-6h, and the ball milling rotating speed is 260-580 r/min.
The surface humation-like zero-valent iron is applied to removing heavy metals and organic pollutants in water.
The application is that the addition amount of the surface humation zero-valent iron is 0.2-1g/L, and the mechanical stirring speed is 200 r/min.
The invention has the beneficial effects that: the zero-valent iron is modified by using the sugar substance by using the ball milling technology, and a layer of humification-like substance is formed on the zero-valent iron shell layer, and the humification-like substance has stronger electron conduction capability and can strengthen the corrosion and electron donating capability of the zero-valent iron, and meanwhile, the humification-like substance can strengthen the adsorption of the zero-valent iron on pollutants, promote the removal of the pollutants, change the surface physical and chemical properties of the zero-valent iron and strengthen the transmission capability of the zero-valent iron. The method has the advantages of simple operation, wide raw material source, low price and no secondary pollution risk. The novel organic-inorganic coupling material is prepared by utilizing a ball milling technology, the cost is far lower than that of the zero-valent iron loaded organic material reported in the prior art, and the pollutant removal efficiency is also far higher than that of the zero-valent iron modified active carbon material reported in the prior art.
Description of the drawings:
FIG. 1a is Scanning Electron Microscope (SEM) results of conventional ball-milled zero-valent iron, and FIG. 1b is SEM results of surface humus-like zero-valent iron of the present invention.
FIG. 2 is a graph showing the comparison of the effect of removing chromium between the ball-milled zero-valent iron and the surface-type humified zero-valent iron in example 1.
FIG. 3 is a graph showing the comparison of the effect of eliminating p-chloronitrobenzene by the ball-milled zero-valent iron and the surface humus-like zero-valent iron in example 2.
Detailed Description
The invention provides the surface humation zero-valent iron with low cost, environmental protection and simple operation, and provides a new method for improving the activity and the transmission performance of the zero-valent iron.
The preparation method of the surface humation zero-valent iron comprises the following steps:
firstly, weighing saccharide substances and zero-valent iron according to a certain mass ratio, and then filling the saccharide substances and the zero-valent iron into a ball milling tank for ball milling to obtain the surface humus-like zero-valent iron material.
The surface humation zero-valent iron is added into a pollutant water body to remove heavy metals and organic pollutants.
According to the scheme, the mass ratio of the saccharides to the zero-valent iron is preferably 1:5-1: 50.
According to the scheme, the ball milling time is preferably 2-6h, and the ball milling rotating speed is 260-.
According to the scheme, the ball-milled surface humation zero-valent iron can be directly used for repairing pollutants in water without other treatment.
According to the scheme, the saccharides comprise monosaccharide, disaccharide and/or polysaccharide substances such as xylose, glucose and/or starch,
according to the scheme, the dosage of the surface humus zero-valent iron for removing heavy metals and organic pollutants in water is preferably 0.2-1g/L, and the mechanical stirring speed is 200 r/min.
The invention has the beneficial effects that: the method utilizes the ball milling technology to modify the zero-valent iron by using the saccharides, forms a layer of carbon material on the zero-valent iron shell layer, constructs a local micro-electrolysis system, can strengthen the corrosion and electron donating capability of the zero-valent iron, promotes the removal of pollutants, changes the surface physical and chemical properties of the zero-valent iron, and enhances the transmission capability of the zero-valent iron.
Several examples are given below to further illustrate the technical scheme of the present invention, and the effect of removing heavy metals and organic pollutants in water by using the surface humus-like zero-valent iron of the present invention and the well-known ball-milled zero-valent iron is compared in the examples.
Example 1
Weighing 5g of zero-valent iron powder and 1g of xylose, setting the ball mill 580 r/min for 2h, and collecting a sample after ball milling, namely the surface humus zero-valent iron, wherein the SEM result is shown in figure 1 b. FIG. 1a shows the SEM result of a conventional ball-milled zero-valent iron. The surface humus-like zero-valent iron of this example was used for hexavalent chromium removal. The concentration of hexavalent chromium is 1mg/L, the adding amount of the surface humus zero-valent iron is 0.2g/L, and the removal rate of the surface humus zero-valent iron to the hexavalent chromium reaches 99.7 percent after the reaction is carried out for 20 min. The chromium removal effect of the ball-milled zero-valent iron and the surface humus-like zero-valent iron added with the same amount is shown in figure 2 in comparison.
Example 2
Weighing 8g of zero-valent iron powder and 0.8g of starch, setting the ball mill to rotate at 260 revolutions per minute for 4 hours, and collecting a sample after ball milling. The surface humus-like zero-valent iron of this example was used for p-chloronitrobenzene removal. The concentration of p-chloronitrobenzene is 28mg/L, the dosage of the surface humus zero-valent iron is 1g/L, and the removal rate of the surface humus zero-valent iron to the p-chloronitrobenzene reaches 99.3 percent after the reaction is carried out for 30 min. The chromium removal effect of the ball-milled zero-valent iron and the surface humus-like zero-valent iron added with the same amount is compared and shown in figure 3.
Example 3
Weighing 10g of zero-valent iron powder and 0.2g of glucose, setting the ball mill to rotate at 550 rpm for 6 hours, and collecting a sample after ball milling. The surface humus-like zero-valent iron of this example was used for hexavalent chromium removal. The concentration of hexavalent chromium is 1mg/L, the adding amount of the surface humus zero-valent iron is 0.5g/L, and the removal rate of the surface humus zero-valent iron to the hexavalent chromium reaches 99.6 percent after the reaction is carried out for 20 min.
Example 4
Weighing 4g of zero-valent iron powder and 0.28g of cellulose, setting the ball mill to rotate at 500 rpm for 3h, and collecting a sample after ball milling. The surface humus-like zero-valent iron of this example was used for p-chloronitrobenzene removal. The concentration of p-chloronitrobenzene is 50mg/L, the dosage of the surface humus zero-valent iron is 1g/L, and the removal rate of the surface humus zero-valent iron to the p-chloronitrobenzene reaches 99.5 percent after the reaction is carried out for 30 min.
Example 5
The surface humus-like zero-valent iron material prepared in example 1 is used for penetration study of quartz sand columns, and the result shows that the transmission distance of the known ball-milling zero-valent iron is 7cm, and the transmission distance of the surface humus-like zero-valent iron is 15 cm.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Surface humation-like zero-valent iron is obtained by the following method:
respectively weighing sugar substances and zero-valent iron according to the mass ratio, then ball-milling by using a ball mill, converting the sugar substances into humoid substances and loading the humoid substances onto a zero-valent iron shell layer to prepare the surface humus-like zero-valent iron.
2. The surface zero-valent humic-like iron of claim 1, wherein the saccharide substance comprises a monosaccharide, disaccharide and/or polysaccharide substance.
3. The surface humus-like zero-valent iron of claim 1, wherein the mass ratio of the saccharide substance to the zero-valent iron is from 1:5 to 1: 50.
4. A method of preparing the surface humified zero-valent iron of claim 1:
respectively weighing sugar substances and zero-valent iron according to the mass ratio, then ball-milling by using a ball mill, converting the sugar substances into humoid to be loaded on a zero-valent iron shell layer, and preparing the surface humus-like zero-valent iron.
5. The method of claim 4, wherein the carbohydrate material comprises a monosaccharide, disaccharide and/or polysaccharide material.
6. The surface zero-valent humic-like iron of claim 4 or 5, wherein the sugar substance comprises xylose, glucose and/or starch.
7. The method according to claim 4, wherein the saccharide is formulated with zero valent iron in a mass ratio of 1:5 to 1: 50.
8. The method as claimed in claim 4, wherein the ball milling time is 2-6h, and the ball milling rotation speed is 260-580 rpm.
9. Use of the surface-humified zero-valent iron of claim 1 for the removal of heavy metals and organic contaminants from water.
10. The use according to claim 9, wherein the surface-humified zero-valent iron is added in an amount of 0.2 to 1g/L and the mechanical stirring speed is 200 revolutions per minute.
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| CN202011010874.7A CN112079417B (en) | 2020-09-23 | 2020-09-23 | Surface humation zero-valent iron and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117884101A (en) * | 2024-01-15 | 2024-04-16 | 华中师范大学 | Chitosan modified zero-valent iron, preparation method thereof, zero-valent iron-based active sand filter filler and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| 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 |
| CN110894084A (en) * | 2019-12-06 | 2020-03-20 | 中国科学技术大学 | Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage |
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- 2020-09-23 CN CN202011010874.7A patent/CN112079417B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| 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 |
| CN110894084A (en) * | 2019-12-06 | 2020-03-20 | 中国科学技术大学 | Nano zero-valent iron load material, preparation method thereof and purification method of hexavalent chromium in sewage |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117884101A (en) * | 2024-01-15 | 2024-04-16 | 华中师范大学 | Chitosan modified zero-valent iron, preparation method thereof, zero-valent iron-based active sand filter filler and application |
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