CN114471725A - Vitamin B12Preparation method and application of zero-valent iron doped composite material - Google Patents

Vitamin B12Preparation method and application of zero-valent iron doped composite material Download PDF

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CN114471725A
CN114471725A CN202210088605.5A CN202210088605A CN114471725A CN 114471725 A CN114471725 A CN 114471725A CN 202210088605 A CN202210088605 A CN 202210088605A CN 114471725 A CN114471725 A CN 114471725A
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vitamin
zero
ball milling
iron
composite material
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CN114471725B (en
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何锋
曹振宇
蔡世超
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Zhejiang Aoshan Environmental Technology Co ltd
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract

The invention discloses a vitamin B12The preparation method of the zero-valent iron-doped composite material is characterized by comprising the following steps: mixing vitamin B12Mixing the powder and iron powder according to a certain proportion, ball-milling to obtain vitamin B12Doping a zero-valent iron composite material; with vitamin B12The mixture of the powder and the iron powder is used as a reference, and the vitamin B in the mixture is calculated by mass percent12The mass percent of the effective components is 0.5-10%, and the mass percent of the iron powder is 90-99.5%. The invention passes vitamin B12Mixing with iron powder, ball milling to obtain vitamin B12The zero-valent iron-doped composite material can be used for in-situ removal and degradation of heavy metal pollutants, pesticides, azo dyes, halogenated organic matters and/or nitro organic matters in underground water and soil, particularly 1, 2-dichloroethane, and has high removal and degradation efficiency.

Description

Vitamin B12Preparation method and application of zero-valent iron doped composite material
Technical Field
The invention relates to the technical field of environmental remediation, in particular to vitamin B12A preparation method and application of a zero-valent iron doped composite material.
Background
Zero-valent iron (ZVI) is a cheap and effective reducing agent that can remove a variety of pollutants from water, including chlorinated organics, nitroarenes, heavy metals, and dyes. In recent years, researchers at home and abroad continuously explore the modification of the surface of zero-valent iron or synthesize composite materials on the basis of the modification, and a plurality of technical ideas are provided. Noble metals (platinum, palladium, silver, etc.) are loaded onto zero-valent iron as Zhang et al to form a bi-metallic material (Treatment of chlorinated organic semiconductors with nano-scale binary composites. Catal. Today.1998,40(4),387 395), while He et al prepare iron-carbon composites using Ball milling (grading of trichloromethane with a Novel Ball Milled Fe-C Nanocomposition. J Hazard Mater 2015,300,443-50), Gu et al (Gu, Y.; Wang, B., F.; Bradley, M.J.; transyek, P.G. Mechalco-colloidal sulfonated micro-crystalline) by mechanical Ball milling with zero-valent iron 12621. Suffolv. S. 35. and U.S. S. 1. U.S. S. Pat. No. 20151. 12653), and He et al synthesize the bi-metallic material by the micro-valent iron Ball milling method (chemical sulfur, U.S. S. 51, 12653). However, these modifications are still difficult to degrade for some refractory halogenated organics such as 1, 2-dichloroethane and the like.
Vitamin B12(VB12) Is a complex organometallic cofactor which plays a crucial role in a variety of biological processes. VB12It also exhibits high catalytic reactivity to a variety of halogenated compounds, such as carbon tetrachloride, tetrachloroethylene, hexachlorobenzene, 2,3,4,5, 6-pentachlorodiphenyl, 2, 6-dichlorophenol, 2',4,4' -tetrabromodiphenyl ether, and the like. Research proves that VB12Reduced state (VB)12Co I) is capable of dehalogenating chlorinated compounds (e.g., trichloroethylene, tetrachloroethylene, etc.) in the presence of strong reducing agents such as titanium citrate. These strong reducing agents act as a large number of electron donors to ensure VB12The central cobalt ion is completely reduced to +1 valence, i.e., the super-reduced B12s state. However, these strong reducing agents have the problems of harsh reaction conditions (high temperature), low electron efficiency and the like, which results in high cost and low site remediation efficiency of the corresponding remediation method.
Therefore, VB can be prepared for the domestic specific pollutants such as 1, 2-dichloroethane12And zero-valent iron.
Disclosure of Invention
The invention combines the technical means of the prior zero-valent iron modification and synthesis to synthesize vitamin B12The preparation method of the zero-valent iron-doped novel composite material has the advantages of rich raw material source, simple and convenient operation and low cost, and the prepared vitamin B12The zero-valent iron-doped composite material has higher removal efficiency on pollutants such as heavy metals, pesticides, azo dyes, halogenated organic matters, nitro organic matters and the like, and particularly 1, 2-dichloroethane can be produced in large scale to meet the requirement of environmental remediation.
The specific technical scheme is as follows:
vitamin B12The preparation method of the zero-valent iron-doped composite material comprises the following steps: mixing vitamin B12Mixing the powder and iron powder according to a certain proportion, ball-milling to obtain vitamin B12Doping a zero-valent iron composite material;
with vitamin B12The mixture of the powder and the iron powder is used as a reference, and the vitamin B in the mixture is calculated by mass percent12Mass percent of active ingredientsThe percentage is 0.05-10%, and the mass percentage of the iron powder is 90-99.95%.
The innovation of the invention is that: by vitamin B12Mixing with iron powder, ball milling to obtain vitamin B12Composite material with uniformly distributed zero-valent iron, and vitamin B in the material12As an electron shuttle for degrading and removing contaminants, the zero-valent iron provides the electrons needed for reducing and degrading the contaminants; more importantly, the vitamin B in the composite material12Becomes vitamin B in the ball milling process12rCan efficiently transfer zero-valent iron to provide electrons so as to complete degradation of halogenated organic matters such as ethylene chloride and the like, and simultaneously is compared with common zero-valent iron and vitamin B12The composite material degraded 1, 2-dichloroethane more stably than the vitamin B in the amount of the corresponding substance (1, 2-dichloroethane removal time 120 hours, degradation efficiency 70%)12And zero-valent iron, the degradation rate is improved by nearly fifty times, and the degradation effective life is prolonged by nearly five times.
The above vitamin B12The zero-valent iron doped composite material can finally convert pollutants into low-pollution or pollution-free products, and is very suitable for in-situ remediation of underground water and soil.
The above method is used for vitamin B12The particle size of the iron powder and the iron powder is not strictly required, but the maximum particle size is not more than 10 mm; preferably less than 1 mm.
Further, the iron powder is simple substance iron powder, reduced iron powder, cast iron powder, raw iron powder or industrial waste iron powder containing zero-valent iron.
Further, the vitamin B12The purity of (A) is 1-99%. Vitamin B used in the invention12Can be vitamin B for cell culture and insect cell culture12Food grade vitamin B12Raw material, or feed grade vitamin B12Raw materials. Preferably, vitamin B12The purity of the powder is 1% or 99%; or, vitamin B12The purity of (A) is 99% or more.
Further preferably, vitamin B is added12Mixture of powder and iron powder as reference by massIn percentage, vitamin B in the mixture12The mass percent of the effective components is 2.5-5%, and the mass percent of the iron powder is 95-97.5%.
Further, the ball milling mode is dry ball milling, and the dry ball milling comprises planetary ball milling, vibration ball milling, stirring ball milling, drum ball milling, horizontal ball milling and dry sanding; the adopted ball milling medium is iron ball, steel ball, ceramic ball, agate ball, silicon nitride ball or zirconia ball; the grain diameter of the ball milling medium is 0.5 mm-10 mm; the filling amount of the ball milling medium is 10-50% by volume of the ball milling tank or the ball milling cavity of the mixer.
Further, vitamin B is added12Mixing the iron powder and the iron powder, then putting the mixture into a ball milling tank, filling a ball milling medium into the ball milling tank, and then carrying out dry ball milling; after the ball milling is finished, separating the ball milling medium to obtain vitamin B12Doping a zero-valent iron composite material; the rotation speed of the dry ball milling is 100-1000 rpm, and the time is 0.5-30 hours.
Preferably, the vitamin B of the invention12The preparation method of the zero-valent iron-doped composite material comprises the following steps: vitamin B is mixed by a planetary ball (dry) mill12(the purity is 99 percent) and iron powder are mixed in a ball milling tank according to the dosage (mass fraction) of 5 percent and 95 percent; the ball milling tank is filled with ball milling media which account for 10-50% of the volume of the ball milling tank, and the ball milling tank is in an inert gas atmosphere; starting the ball mill, adjusting the rotation speed of the ball mill to 300-800 rpm, continuously ball-milling for 5-30 hours, and separating a ball-milling medium and a ball-milling product under the condition of nitrogen atmosphere after ball-milling is finished to obtain the vitamin B12Doping a zero-valent iron composite material; the particle size of the iron powder is less than 100 mu m; the ball milling medium is an iron ball, a steel ball, a silicon nitride ball or a zirconia ball with the diameter of 6 mm.
The invention also provides vitamin B prepared by the preparation method12Doping the zero-valent iron composite material.
Further, the vitamin B12The zero-valent iron-doped composite material takes zero-valent iron as an inner core and vitamin B on the surface12Vitamin B12The central cobalt ion of (a) exhibits valence 3, 2 and 0 states.
The invention also provides the vitamin B12The zero-valent iron-doped composite material is applied to the treatment of wastewater and polluted soil, wherein the wastewater, the polluted soil and the polluted underground water contain at least one of heavy metals, pesticides, azo dyes, halogenated organic matters and nitro-substituted organic matters.
Further, the heavy metals include, but are not limited to, hexavalent chromium (cr (vi)), cadmium (Cd), nickel (Ni), mercury (Hg), manganese (Mn), arsenic (As), antimony (Sb), lead (Pb), and the like; the pesticide includes but is not limited to atrazine, dichlorophenoxyacetic acid, polychlorinated biphenyl, dichlorodiphenyl, and the like; the azo dyes include, but are not limited to, sudan red, orange G, golden orange II; halogenated organics include, but are not limited to, carbon tetrachloride, tetrachloroethane, chloroform, tetrachloroethylene, trichloroethylene, 1, 2-dichloroethane; the nitroaromatics include, but are not limited to, nitrobenzene.
Further, the wastewater-contaminated soil and the contaminated groundwater contain halogenated organic matters; 1, 2-dichloroethane is preferred.
Further, the vitamin B12When the zero-valent iron-doped composite material is used for treating wastewater, the pH value of the wastewater can be adjusted firstly
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses vitamin B12Mixing with iron powder, ball milling to obtain vitamin B12The zero-valent iron-doped composite material can be used for in-situ removal and degradation of heavy metal pollutants, pesticides, azo dyes, halogenated organic matters and/or nitro organic matters in underground water and soil, particularly 1, 2-dichloroethane, and has high removal and degradation efficiency.
(2) The preparation method is simple, and the vitamin B can be obtained only by simple ball milling12The zero-valent iron composite material is doped, toxic and harmful chemical raw materials are not used in the preparation process, no waste liquid is generated, no dangerous gas is generated, the cost of the raw materials is low, and the method belongs to an environment-friendly process.
(3) Vitamin B prepared by the method of the invention12Degradation of zero-valent iron-doped composite materialAnd high activity for removing pollutants, high stability and durability when applied to underground water, and can solve vitamin B12Easy loss and poor stability in-situ repair.
(4) Aiming at the problem that most of pollutants in domestic polluted sites are 1, 2-dichloroethane, the technical bottleneck that the 1, 2-dichloroethane cannot be degraded by a non-biological in-situ treatment technology is broken through, and compared with a biological degradation technology, the method has the advantages of short repair period, low maintenance cost and the like.
Drawings
FIG. 1 shows vitamin B prepared in example 112SEM-EDS picture of the zero-valent iron doped composite material;
wherein A is a material scanning electron microscope image; b is a distribution diagram of iron element of the material; c is the distribution diagram of the cobalt element of the material.
FIG. 2 shows vitamin B12Cobalt element X-ray photoelectron spectrum and vitamin B prepared in example 112An X-ray photoelectron energy spectrum of the zero-valent iron-doped composite material.
FIG. 3 is vitamin B prepared in example 112An X-ray photoelectron spectrum of the cobalt element doped with the zero-valent iron composite material.
FIG. 4 shows vitamin B prepared in example 112Kinetic diagram of degradation of 1, 2-dichloroethane by doped zero-valent iron composite material.
FIG. 5 shows vitamin B prepared in example 112Kinetic diagram of degrading trichloroethylene by doping zero-valent iron composite material.
FIG. 6 shows vitamin B prepared in example 112Kinetic diagram of the doped zero-valent iron composite material for degrading tetrachloroethylene.
FIG. 7 shows vitamin B in the ball milling in comparative example 112Kinetic diagram for the adsorption of 1, 2-dichloroethane.
FIG. 8 is a kinetic diagram of adsorption of 1, 2-dichloroethane by the ball-milled zero-valent iron in comparative example 2.
FIG. 9 shows the original zero-valent iron and vitamin B in comparative example 312Kinetic diagram for the adsorption of 1, 2-dichloroethane.
FIG. 10 is a graph showing the kinetics of long-term degradation of 1, 2-dichloroethane by vitamin B12 doped with zero-valent iron composite in example 4.
FIG. 11 is a graph showing the kinetics of degradation of 1, 2-dichloroethane by vitamin B12 doped zero-valent iron composite under different pH conditions in example 5.
FIG. 12 is a graph of the kinetics of degradation of 1, 2-dichloroethane with vitamin B12 doped zero valent iron composite aged over 30 days in simulated groundwater in example 6.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are only illustrative of the present invention, but the scope of the present invention is not limited thereto.
Example 1
Vitamin B production Using a planetary ball mill (Dry ball mill)12The zero-valent iron-doped composite material comprises the following steps:
(1) filling zirconia ball milling beads (with the particle size of 6mm) into a ball milling tank as a ball milling medium, wherein the filling amount is 20% of the volume of the ball milling tank;
(2) mixing 0.125g vitamin B with purity of 99%12Respectively 5% of powder and 2.475g of iron powder (the particle size is less than 1mm) in mass fraction, filling 95% of the powder into a ball milling tank, uniformly mixing, and filling nitrogen into the tank;
(3) adjusting the rotation number of the ball mill to 400rpm, and continuously ball-milling for 20 hours;
(4) under the protection of nitrogen, separating the ball milling medium from the ball milling product by using a screen to obtain the carbon-sulfur doped zero-valent iron composite material.
As can be seen from FIG. 1, vitamin B was physically ball milled12The coating is effectively attached to the surface of the zero-valent iron and is uniformly distributed; as can be seen from FIGS. 2 to 3, vitamin B was physically ball-milled12The structure of (a) is chemically changed, wherein the cobalt ion shows 3-valent, 2-valent and 0-valent states.
The activity of the above materials was tested with 1, 2-dichloroethane as the target contaminant. 0.26g vitamin B was added to a 52mL reagent bottle12Doping a zero-valent iron composite material, adding 26mL of deoxidized ultrapure water, covering tightly by using an aluminum cover with a PTFE (polytetrafluoroethylene) spacer, then adding 1, 2-dichloroethane stock solution to ensure that the initial concentration of the 1, 2-dichloroethane is 10ppm,the vial was then placed on a shaker and shaken, maintaining a constant temperature of 25 ℃.
As a result: after 8 hours of reaction, the concentration of 1, 2-dichloroethane was measured to be 0ppm, and the degradation rate was 100% (as shown in FIG. 4).
Trichloroethylene and tetrachloroethylene are respectively used as target pollutants, wherein the trichloroethylene concentration is measured to be 0ppm and the degradation rate is 100% after the trichloroethylene reacts for 48 hours, and the trichloroethylene concentration is measured to be 0.12ppm and the degradation rate is 98.8% after the tetrachloroethylene reacts for 90 minutes, as shown in figures 5 and 6.
Example 2
This example was conducted in accordance with example 1, using a planetary ball mill, and vitamin B as a raw material12Powder, reduced iron powder (particle size less than 1mm), tested for the contaminant 1, 2-dichloroethane, and other technical parameters and results are shown in table 1 below:
TABLE 1
Figure BDA0003488253000000051
Figure BDA0003488253000000061
Example 3
This example was conducted in accordance with example 1, using a planetary ball mill, and vitamin B as a raw material12Reduced iron powder (particle size less than 1mm), aiming at other typical pollutants, the other technical parameters and results are shown in the following table:
Figure BDA0003488253000000062
Figure BDA0003488253000000071
comparative example 1
By means of planetary ballsPreparation of ball-milled vitamin B by mill (dry ball mill)12The method comprises the following steps:
(1) filling zirconia ball milling beads (with the particle size of 6mm) into a ball milling tank as a ball milling medium, wherein the filling amount is 20% of the volume of the ball milling tank;
(2) mixing 0.5g vitamin B12(purity 99%) was placed in a tank and the tank was filled with nitrogen;
(3) adjusting the rotation number of the ball mill to 400rpm, and continuously ball-milling for 20 hours;
(4) under the protection of nitrogen, separating the ball milling medium from the ball milling product by using a screen to obtain ball milling vitamin B12。
The activity of the above materials was tested with 1, 2-dichloroethane as the target contaminant. 0.0013g of ball milling vitamin B is added into a 52mL reagent bottle12(corresponding to vitamin B used in example 1)12Vitamin B doped with zero-valent iron composite material12) 26mL of deoxygenated ultrapure water was added, the flask was closed with an aluminum cap with a PTFE septum, then the stock solution of 1, 2-dichloroethane was added to ensure an initial concentration of 1, 2-dichloroethane of 10ppm, and then the flask was set on a shaker and shaken to maintain a constant temperature of 25 ℃.
After 72 hours of reaction, the concentration of 1, 2-dichloroethane was measured to be 9.7ppm, and the removal rate was 3% (as shown in FIG. 7). However, this process did not detect any degradation products. So that only physical adsorption occurs, vitamin B12And does not effectively degrade 1, 2-dichloroethane.
Comparative example 2
The ball-milling zero-valent iron is prepared by adopting a planetary ball mill (dry ball mill) and comprises the following steps:
(1) filling zirconia ball milling beads (with the particle size of 6mm) into a ball milling tank as a ball milling medium, wherein the filling amount is 20% of the volume of the ball milling tank;
(2) 2.5g of zero-valent iron powder (the particle size is less than 1mm) is placed in a tank, and the tank is filled with nitrogen;
(3) adjusting the rotation number of the ball mill to 400rpm, and continuously ball-milling for 20 hours;
(4) under the protection of nitrogen, separating the ball milling medium from the ball milling product by using a screen to obtain ball milling zero-valent iron.
The activity of the above materials was tested with 1, 2-dichloroethane as the target contaminant. 0.26g of ball-milled zero-valent iron was added to a 52mL reagent bottle, 26mL of deoxygenated ultrapure water was added, the bottle was closed with an aluminum cap with a PTFE septum, then 1, 2-dichloroethane stock solution was added to ensure that the initial concentration of 1, 2-dichloroethane was 10ppm, and then the reagent bottle was set on a shaker and shaken to maintain a constant temperature of 25 ℃.
After 196 hours of reaction, the concentration of 1, 2-dichloroethane was measured to be 9.3ppm, and the degradation rate was 7% (as shown in FIG. 8). However, this process did not detect any degradation products. Therefore, only physical adsorption is carried out, and 1, 2-dichloroethane cannot be effectively degraded by ball milling zero-valent iron.
Comparative example 3
Testing original zero-valent iron and vitamin B by taking 1, 2-dichloroethane as a target pollutant12And (4) reaction effect. A52 mL reagent bottle was charged with 0.247g of raw zero valent iron and 0.013 vitamin B12(corresponding to vitamin B used in example 1)12Doped with zero-valent iron composite material), 26mL of deoxidized ultrapure water is added, an aluminum cover with a PTFE spacer is used for covering tightly, then 1, 2-dichloroethane stock solution is added to ensure that the initial concentration of 1, 2-dichloroethane is 10ppm, and then a reagent bottle is placed on an oscillator for oscillation, and the constant temperature of 25 ℃ is kept.
After 72 hours of reaction, the 1, 2-dichloroethane concentration was measured to be 0.49ppm, and the degradation rate was 51% (as shown in FIG. 9).
Example 4
Vitamin B in this example12The zero-valent iron doped composite was prepared in accordance with example 1.
The long-term effectiveness of the above materials was tested with 1, 2-dichloroethane as the target contaminant. 0.26g vitamin B was added to a 52mL reagent bottle12Doping a zero-valent iron composite material, adding 26mL of deoxidized ultrapure water, covering tightly by using an aluminum cover with a PTFE (polytetrafluoroethylene) spacer, then adding 1, 2-dichloroethane stock solution to ensure that the initial concentration of the 1, 2-dichloroethane is 10ppm, then placing a reagent bottle on an oscillator for oscillation, and keeping the constant temperature of 25 ℃. After every few days, 10ppm1, 2-dichloroethane stock solution was added to ensure long-term degradation of the material.
As a result: after 31 days of reaction, the 1, 2-dichloroethane concentration was measured to be 0ppm, demonstrating that the material still retains a higher activity in the case of long-term degradation of 1, 2-dichloroethane (as shown in FIG. 10).
Example 5
This example vitamin B12 doped zero valent iron composite was prepared in accordance with example 1.
The long-term effectiveness of the above materials was tested with 1, 2-dichloroethane as the target contaminant. 0.26g of vitamin B12-doped zero-valent iron composite material was added to a 52mL reagent bottle, 26mL of deoxygenated ultrapure water formulated to different pH values were added, respectively, (0.1 mol/L NaOH or HCl solution for pH adjustment) was covered tightly with an aluminum cap with a PTFE spacer, then 1, 2-dichloroethane stock solution was added to ensure an initial concentration of 1, 2-dichloroethane of 10ppm, and then the reagent bottle was set on a shaker and shaken to maintain a constant temperature of 25 ℃.
It can be seen that the degradation rate of the material for 1, 2-dichloroethane increases under different pH conditions, wherein the degradation rate reaches 100% after 4 hours under the pH11 condition, and the degradation rates of the rest of the pH10, 8, 7, 6 and 4 are respectively 100%, 99%, 94%, 93% and 100% after 6 hours (as shown in FIG. 11).
Example 6
Vitamin B in this example12The zero-valent iron doped composite was prepared in accordance with example 1.
To test the long term effectiveness of the material in simulated groundwater, 0.26g vitamin B was added to a 52ml reagent bottle12Doping a zero-valent iron composite material, adding 26mL of simulated underground water solution, standing for 30 days, keeping the material in a reagent bottle, pouring out the solution, adding 26mL of deoxidized ultrapure water, tightly covering with an aluminum cover with a PTFE (polytetrafluoroethylene) spacer, adding 1, 2-dichloroethane stock solution to ensure that the initial concentration of 1, 2-dichloroethane is 10ppm, then placing the reagent bottle on an oscillator for oscillation, and keeping the constant temperature of 25 ℃.
After 120 hours of reaction, the 1, 2-dichloroethane concentration was measured to be 0.04ppm, and the degradation rate was 96% (as shown in FIG. 11).

Claims (10)

1. Vitamin B12Doping zero valenceThe preparation method of the iron composite material is characterized by comprising the following steps: mixing vitamin B12Mixing the powder and iron powder according to a certain proportion, ball-milling to obtain vitamin B12Doping a zero-valent iron composite material;
with vitamin B12The mixture of the powder and the iron powder is used as a reference, and the vitamin B in the mixture is calculated by mass percent12The mass percent of the effective components is 0.05-10%, and the mass percent of the iron powder is 90-99.95%.
2. Vitamin B as claimed in claim 112The preparation method of the zero-valent iron doped composite material is characterized in that the iron powder is simple substance iron powder, reduced iron powder, cast iron powder, raw iron powder or industrial waste iron scrap containing zero-valent iron.
3. Vitamin B as claimed in claim 112The preparation method of the zero-valent iron-doped composite material is characterized in that the vitamin B12The purity of the powder is 1-99%; preferably, vitamin B12The purity of the powder was 1% or 99%.
4. Vitamin B as claimed in claim 112The preparation method of the zero-valent iron-doped composite material is characterized in that vitamin B is used12The mixture of the powder and the iron powder is used as a reference, and the vitamin B in the mixture is calculated by mass percent12The mass percent of the effective components is 2.5-5%, and the mass percent of the iron powder is 95-97.5%.
5. Vitamin B as claimed in claim 112The preparation method of the zero-valent iron doped composite material is characterized in that the ball milling mode is dry ball milling, and the dry ball milling comprises planetary ball milling, vibration ball milling, stirring ball milling, drum ball milling, horizontal ball milling and dry sand milling; the adopted ball milling medium is iron ball, steel ball, ceramic ball, agate ball, silicon nitride ball or zirconia ball; the grain diameter of the ball milling medium is 0.5 mm-10 mm; based on the volume of a ball milling cavity of a ball milling tank or a mixer, the ball millingThe filling amount of the medium is 10-50%.
6. Vitamin B as claimed in claim 112The preparation method of the zero-valent iron-doped composite material is characterized in that vitamin B is added12Mixing the iron powder and the iron powder, then putting the mixture into a ball milling tank, filling a ball milling medium into the ball milling tank, and then carrying out dry ball milling; after the ball milling is finished, separating the ball milling medium to obtain vitamin B12Doping a zero-valent iron composite material; the rotation speed of the dry ball milling is 100-1000 rpm, and the time is 0.5-30 hours.
7. Vitamin B produced by the production method according to any one of claims 1 to 612Doping the zero-valent iron composite material.
8. Vitamin B as claimed in claim 712Zero-valent iron-doped composite material, characterized in that the vitamin B12The zero-valent iron-doped composite material takes zero-valent iron as an inner core and vitamin B on the surface12Vitamin B12The central cobalt ion of (a) exhibits valence 3, 2 and 0 states.
9. Vitamin B as claimed in claim 712The application of the zero-valent iron-doped composite material in treating wastewater, polluted soil and polluted groundwater is characterized in that the wastewater and the polluted soil contain at least one of heavy metals, pesticides, azo dyes, halogenated organic matters and nitro-substituted organic matters.
10. The use of claim 9, wherein the wastewater, contaminated soil and contaminated groundwater contains halogenated organics; 1, 2-dichloroethane in wastewater and contaminated soil is preferred.
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CN106669586A (en) * 2016-12-29 2017-05-17 中南大学 Fe@FeS2 composite material, and preparation method and application thereof
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CN106536097A (en) * 2015-11-06 2017-03-22 浙江工业大学 Preparation method of iron-ferrous sulfide complex
CN106669586A (en) * 2016-12-29 2017-05-17 中南大学 Fe@FeS2 composite material, and preparation method and application thereof
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