CN112139508A - Amphoteric surface micron zero-valent iron, and preparation method and application thereof - Google Patents
Amphoteric surface micron zero-valent iron, and preparation method and application thereof Download PDFInfo
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- CN112139508A CN112139508A CN202011010897.8A CN202011010897A CN112139508A CN 112139508 A CN112139508 A CN 112139508A CN 202011010897 A CN202011010897 A CN 202011010897A CN 112139508 A CN112139508 A CN 112139508A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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Abstract
An amphoteric surface micron zero-valent iron is obtained by the following method: firstly, respectively weighing alkali metal salt, a surfactant and micron zero-valent iron according to the mass ratio, then carrying out ball milling, and modifying the surfactant to the surface of the micron zero-valent iron to obtain a target product. The micron zero-valent iron with the amphoteric surface is prepared by modifying the micron zero-valent iron with the surfactant, so that the pollutant removing capability of the micron zero-valent iron is improved, and the mobility of the micron zero-valent iron in an aquifer is improved.
Description
Technical Field
The invention belongs to the field of preparation and application of underground water repairing materials, and particularly relates to micron zero-valent iron with an amphoteric surface.
The invention also relates to a preparation method of the amphoteric surface micron zero-valent iron.
The invention also relates to application of the amphoteric surface micron zero-valent iron in removing pollutants in underground water.
Background
With the rapid development of industry and agriculture, the pollution of underground water is more and more serious, and the pollutants mainly comprise heavy metals and organic matters. The contaminated ground water seriously affects the drinking water safety of people. Therefore, efficient and economical remediation techniques must be developed for the prevention and control of groundwater pollution.
The existing groundwater remediation technology is divided into an in-situ remediation technology and an ex-situ remediation technology according to the remediation position. Compared with the ectopic repair technology, the in-situ repair technology has the advantages of small disturbance, small occupied area, low cost and the like and is widely concerned and applied. The core of the in-situ repair technology lies in the selection of repair materials, wherein zero-valent iron is applied as a reduction type repair core repair material. However, the zero-valent iron is found to have the following problems in the use process, such as easy passivation and inactivation and weak migration capacity, and the problems greatly limit the comprehensive popularization and application of the zero-valent iron. In order to solve the problems, researchers load zero-valent iron on activated carbon, molecular sieves, carboxymethyl cellulose and natural clay minerals to prepare the loaded nano zero-valent iron. Although the loading strategy can improve the pollutant removal effect and the migration capacity of the nano zero-valent iron, the preparation process of the material is complicated, the cost is too high, and the application of the technology is severely limited.
More and more researches show that the effect of removing pollutants by using micron zero-valent iron can be remarkably improved through modification, such as acid washing, magnetic field strengthening, active carbon adding and the like. However, whether the methods can continuously improve the pollutant removal effect and the migration capacity of the micron zero-valent iron is unknown. It is known that the key of in-situ injection of zero-valent iron is that the zero-valent iron can effectively migrate to the pollution plume region, contact with the pollutants and react with the pollutants. While the mobility of zero-valent iron is related to the chemical composition and structure of its surface interface. Therefore, the invention provides a mode for changing the chemical composition and the structure of the surface interface of the micron zero-valent iron, and the mobility and the pollutant removal capability of the micron zero-valent iron in an aquifer medium are improved.
Disclosure of Invention
The invention aims to provide the micron zero-valent iron with the amphoteric surface.
Still another object of the present invention is to provide a method for preparing the above amphoteric surface micron zero-valent iron.
The invention further aims to provide application of the amphoteric surface micron zero-valent iron in removing pollutants in groundwater.
In order to achieve the purpose, the amphoteric surface micron zero-valent iron provided by the invention is obtained by the following method:
firstly, respectively weighing alkali metal salt, a surfactant and micron zero-valent iron according to the mass ratio, then carrying out ball milling, and modifying the surfactant to the surface of the micron zero-valent iron to obtain a target product.
The invention provides a method for preparing the amphoteric surface micron zero-valent iron, which comprises the following steps:
firstly, respectively weighing alkali metal salt, a surfactant and micron zero-valent iron according to the mass ratio, then carrying out ball milling, and modifying the surfactant to the surface of the micron zero-valent iron to prepare the amphoteric surface micron zero-valent iron.
The method of (a), wherein the alkali metal salt is a sodium salt and/or a potassium salt; the surface active agent is cationic surfactant, anionic surfactant and/or nonionic surfactant; the micron zero-valent iron is scrap iron and/or commercial zero-valent iron.
The method comprises the following steps of mixing alkali metal salt, surfactant and micron zero-valent iron according to a mass ratio of 0.1:1-10: 1-100.
The method comprises the steps that the ball milling time is 1-5h, and the ball milling rotating speed is 300-550 r/min.
The application of the amphoteric surface micron zero-valent iron in removing pollutants in underground water comprises the following steps: adding 0.1-1g/L of amphoteric surface micron zero-valent iron into underground water containing heavy metal or organic pollutant.
The application, wherein, the adding mode is in-situ injection.
The invention has the beneficial effects that: the micron zero-valent iron with the amphoteric surface is prepared by modifying the micron zero-valent iron with the surfactant, so that the pollutant removing capability of the micron zero-valent iron is improved, and the mobility of the micron zero-valent iron in an aquifer is improved.
Description of the drawings:
FIG. 1 shows the dechroming effect of ball-milled zero-valent iron and amphoteric surface micron zero-valent iron (example 1).
FIG. 2 shows the effect of ball milling zero-valent iron and amphoteric surface micron zero-valent iron on p-chloronitrobenzene removal (example 2).
Detailed Description
The invention provides a preparation method of amphoteric surface micron zero-valent iron with simple preparation, economy, high efficiency and ecological environmental protection and application thereof, and provides a new method for strengthening the pollutant removal capability and the migration capability of the zero-valent iron in an aquifer.
The technical scheme adopted by the invention is as follows:
1) firstly, weighing alkali metal salt, surfactant and micron zero-valent iron (the micron zero-valent iron is powder which is ground into micron-sized by scrap iron and/or commercial zero-valent iron in advance) according to the mass ratio, and then ball-milling by using a ball mill to finally obtain the amphoteric surface micron zero-valent iron.
2) And injecting the micron zero-valent iron with the amphoteric surface into a pollution plume region to remove heavy metals and organic pollutants.
According to the scheme, the mass ratio of the alkali metal salt, the surfactant and the zero-valent iron is 0.1:1-10: 1-100.
According to the scheme, the ball milling time is 1-5h, and the ball milling rotating speed is 300-550 r/min.
According to the scheme, the material after ball milling is directly used for pollutant remediation without other treatment.
According to the scheme, the surfactant comprises one or more of cationic surfactant, anionic surfactant and nonionic surfactant.
According to the scheme, the suspension with the addition amount of 0.1-1g/L of the micron zero-valent iron on the amphoteric surface is injected into the pollution plume area in an in-situ injection mode.
The amphoteric surface micron zero-valent iron powder and the ball-milled zero-valent iron are used for quartz sand column penetration research, the transmission distance of the amphoteric surface zero-valent iron is 9cm, the transmission distance of the ball-milled zero-valent iron is 3cm, and the removal rate is improved by 87 times.
The invention is further described below with reference to the following figures and examples.
Example 1
Firstly, 0.04g of potassium chloride, 0.4g of cationic surfactant and 4g of micron zero-valent iron powder are weighed, the parameters of a ball mill are set to be 550 revolutions per minute, the time is 2 hours, a sample of the micron zero-valent iron powder on the amphoteric surface is collected after ball milling and is injected into a pollution plume area for removing hexavalent chromium in water, the concentration of the hexavalent chromium is 2mg/L, the adding amount of the micron zero-valent iron on the amphoteric surface is 0.2g/L, and after 20 minutes of reaction, the removal rate of the hexavalent chromium reaches 95.6%.
For comparison, the amphoteric surface micron zero-valent iron powder is changed into the original zero-valent iron, the adding amount is 0.2g/L, and the removal rate is only 0.5%. Compared with the prior art, the removal rate of the method is improved by 180 times.
The comparative effect is shown in fig. 1.
Example 2
Firstly, 0.08g of sodium chloride, 0.8g of anionic surfactant and 8g of micron zero-valent iron powder are weighed, the parameters of a ball mill are set to be 300 revolutions per minute, the time is 4 hours, a sample of the micron zero-valent iron powder on the amphoteric surface is collected after ball milling and is injected into a pollution plume area for removing p-chloronitrobenzene in water, the concentration of the p-chloronitrobenzene is 28mg/L, the adding amount of the zero-valent iron on the amphoteric surface is 2g/L, and after 30min of reaction, the removal rate of the p-chloronitrobenzene reaches 96.3%.
For comparison, the amphoteric surface micron zero-valent iron powder is changed into the original zero-valent iron, the adding amount is 2g/L, the removal rate is only 35%, and compared with the original zero-valent iron powder and the original zero-valent iron powder, the removal rate is improved by 40 times.
The comparative effect is shown in fig. 2.
Example 3
Firstly, 0.01g of sodium sulfate, 0.1g of nonionic surfactant and 10g of micron zero-valent iron powder are weighed, the parameters of a ball mill are set to be 550 revolutions per minute, the time is 6 hours, a sample of the micron zero-valent iron powder on the amphoteric surface is collected after ball milling and is injected into a pollution plume area for removing hexavalent chromium in water, the concentration of the hexavalent chromium is 1mg/L, the adding amount of the zero-valent iron on the amphoteric surface is 1g/L, and after reaction is carried out for 30 minutes, the removal rate of the hexavalent chromium reaches 95.2%.
For comparison, the amphoteric surface micron zero-valent iron powder is changed into the original zero-valent iron, the adding amount is 1g/L, the removal rate is only 1%, and compared with the two, the removal rate of the invention is improved by 123 times.
Example 4
Firstly, 0.04g of sodium sulfate, 0.4g of nonionic surfactant and 8g of micron zero-valent iron powder are weighed, the parameters of a ball mill are set to be 500 revolutions per minute, the time is 3 hours, a sample of the micron zero-valent iron powder on the amphoteric surface is collected after ball milling and is injected into a pollution plume area for removing p-chloronitrobenzene in water, the concentration of the p-chloronitrobenzene is 50mg/L, the adding amount of the micron zero-valent iron on the amphoteric surface is 2g/L, and after 30min of reaction, the removal rate of the p-chloronitrobenzene reaches 95.1%.
For comparison, the amphoteric surface micron zero-valent iron powder is changed into the original zero-valent iron, the adding amount is 2g/L, and the removal rate is only 35%.
Claims (7)
1. An amphoteric surface micron zero-valent iron is obtained by the following method:
firstly, respectively weighing alkali metal salt, a surfactant and micron zero-valent iron according to the mass ratio, then carrying out ball milling, and modifying the surfactant to the surface of the micron zero-valent iron to obtain a target product.
2. A method of making the amphoteric surface micron zero valent iron of claim, comprising the steps of:
firstly, respectively weighing alkali metal salt, a surfactant and micron zero-valent iron according to the mass ratio, then carrying out ball milling, and modifying the surfactant to the surface of the micron zero-valent iron to prepare the amphoteric surface micron zero-valent iron.
3. The process according to claim 2, wherein the alkali metal salt is a sodium salt and/or a potassium salt; the surface active agent is cationic surfactant, anionic surfactant and/or nonionic surfactant; the zero-valent iron is scrap iron and/or commercial zero-valent iron.
4. The method of claim 2, wherein the alkali metal salt, the surfactant and the micro zero valent iron are in a mass ratio of 0.1:1 to 10:1 to 100.
5. The method as claimed in claim 2, wherein the ball milling time is 1-5h, and the ball milling rotation speed is 300-.
6. Use of the amphoteric surface micron zero-valent iron of claim 1 for removing contaminants from groundwater: adding 0.1-1g/L of amphoteric surface micron zero-valent iron into underground water containing heavy metal or organic pollutant.
7. The use of claim 6, wherein the additive is an in-situ implant.
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Application publication date: 20201229 |