CN106536097B - Preparation method of iron-ferrous sulfide complex - Google Patents
Preparation method of iron-ferrous sulfide complex Download PDFInfo
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- CN106536097B CN106536097B CN201680001438.9A CN201680001438A CN106536097B CN 106536097 B CN106536097 B CN 106536097B CN 201680001438 A CN201680001438 A CN 201680001438A CN 106536097 B CN106536097 B CN 106536097B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- 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
- 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
Abstract
A preparation method of an iron-ferrous sulfide complex comprises the following steps: mixing elemental sulfur powder and ferrous sulfide powder in a mass ratio of 1: 5-60 or pyrite powder and micron-sized iron powder in a mass ratio of 1: 5-60 to obtain a mixed raw material, placing the mixed raw material in a ball milling tank of a ball mill, filling a grinding medium in the ball milling tank, starting the ball mill in a vacuum environment or an inert gas atmosphere in the ball milling tank, grinding at a grinding speed of 400-4000 rpm for 2-30 hours, and separating the grinding medium from a product after grinding to obtain an iron-ferrous sulfide complex with a particle size of less than 10 microns. The preparation method is simple, the raw material cost is low, toxic and harmful dangerous chemicals are not used or generated, and the prepared iron-ferrous sulfide complex can efficiently purify chlorine-containing organic pollutants and heavy metals in water, and is particularly suitable for in-situ remediation of polluted groundwater.
Description
(I) technical field
The invention relates to a preparation method of an iron-ferrous sulfide complex, in particular to a preparation method of an efficient and environment-friendly iron-ferrous sulfide complex.
(II) background of the invention
Zero-valent iron is a new underground water in-situ remediation technology and has gained wide attention at home and abroad. However, zero-valent iron has many problems in the practical application process, such as aggregation of the zero-valent iron into large particles due to strong magnetism and high surface energy, so that part of active sites cannot be effectively released, and the utilization rate of active ingredients is low; meanwhile, a layer of compact oxide film on the surface of the zero-valent iron can greatly hinder the contact of active ingredients and target pollutants, so that the activity of the zero-valent iron is reduced; in addition, hydrophilic zero-valent iron has poor affinity for hydrophobic organic contaminants in solution.
In order to overcome the defects of the pure zero-valent iron in practical application, domestic and foreign scholars continuously try to modify the surface of the zero-valent iron or compound the surface of the zero-valent iron with other substances. For example, Zhang et al [ Treatment of chlorinated organic pollutants with nanoscopic biological particles. Catal. today.1998,40 (4); 387 395.] loads noble metals such as Pt, Pd, Ag, etc. on zero-valent iron, the rate of degradation of organic pollutants by zero-valent iron is increased by several times, and the degradation products are simpler. Although noble metals such as platinum, palladium, silver and the like can obviously improve the activity of zero-valent iron, the cost is higher, and secondary pollution is easily caused when the noble metals are lost into an environmental medium.
In recent years, ferrous sulfide has become a new type of modifier for zero-valent iron, and studies have found that the presence of ferrous sulfide can greatly enhance the degradation activity of zero-valent iron to pollutants [ Enhanced reduced chlorination iron by sulfuric acid catalyzed nanoscaler ion 2015,78, 144-53; ACS apple screw Interfaces 2011,3(5),1457-62. This is mainly due to two points: (1) the hydrophobicity of the ferrous sulfide enables the ferrous sulfide modified zero-valent iron to be more easily combined with organic pollutants; (2) ferrous sulfide is a semiconductor, and the existence of the ferrous sulfide can greatly improve the transfer efficiency of electrons from zero-valent iron to target pollutants. Therefore, the ferrous sulfide modified zero-valent iron has wide application prospect in the field of repairing the actual polluted water body. However, the existing zero-valent iron-loaded ferrous sulfide or the combination of the zero-valent iron and the ferrous sulfide is prepared by a chemical method, and the preparation method is roughly divided into two types: firstly, reducing a precursor (ferrous salt) of iron into zero-valent iron by borohydride, then adding sulfide, wherein the sulfide can form ferrous sulfide with residual ferrous ions to precipitate on the surface of the zero-valent iron, and finally forming the zero-valent iron load ferrous sulfide. Secondly, adding the borohydride solution containing hydrosulfite into the iron salt solution to form a zero-valent iron and ferrous sulfide complex. Although the compound of iron and ferrous sulfide prepared by a chemical method has smaller particles, the preparation process has a plurality of defects: (1) the synthetic method is relatively complicated; (2) iron is easily oxidized in the synthesis process; (3) the raw material cost is high, and a large amount of waste water is generated; (4) borohydride can generate hydrogen, and the synthesis process has certain danger.
Disclosure of the invention
The invention aims to overcome the defects of the existing chemical method for preparing the iron-ferrous sulfide complex and provide a physical preparation method of the iron-ferrous sulfide complex, which has simple, efficient, clean and safe preparation process.
The invention discloses a physical preparation method of an iron-ferrous sulfide complex, which is simple, efficient, clean and safe and can effectively overcome the defect that the prior art adopts a chemical method to prepare the iron-ferrous sulfide complex.
The technical scheme adopted by the invention is as follows:
a preparation method of an iron-ferrous sulfide complex comprises the following steps: the iron-ferrous sulfide composite is prepared by mixing elemental sulfur powder or iron sulfide powder or iron pyrite powder with micron-sized iron powder in a mass ratio of 1: 5-60, placing the obtained mixed raw material into a ball milling tank of a ball mill, filling a grinding medium into the ball milling tank, starting the ball mill in a vacuum environment or inert gas atmosphere, grinding at a grinding speed of 400-4000 rpm for 2-30 hours, and separating the grinding medium from a product after grinding.
The micron-sized iron powder is the iron powder with the particle size less than 100 microns and can be directly purchased and obtained in the market.
The iron sulfide can be ferrous disulfide, ferrous sulfide, ferric trisulfide, etc.
The pyrite can be pyrite, pyrrhotite, marcasite, sulfur concentrate, Mackinawite (Mackinawite), and the like.
The ball mill can be a planetary ball mill, a vibration ball mill, a sand mill and the like.
The ball milling tank is internally provided with a grinding medium, and the grinding medium is an iron ball, a steel ball, a silicon nitride ball or a zirconia ball with the diameter of 0.15-10 mm, preferably the zirconia ball or the silicon nitride ball.
The loading amount of the grinding medium is generally 10-50%, preferably 15-20% of the volume of the cavity of the ball milling tank.
The ball milling tank is in an inert gas atmosphere or a vacuum environment, preferably in an inert gas atmosphere, and the inert gas can be nitrogen or argon.
The grinding medium and the product are separated after grinding, and the grinding medium and the product can be separated by adopting a screen under the inert gas atmosphere.
The iron-ferrous sulfide complex provided by the invention is powdery particles, and the particle size can be controlled by adjusting the grinding time. The particle size of the iron-ferrous sulfide composite particles prepared by the method is 50 nm-10 mu m.
The mass ratio of the elemental sulfur powder or the iron sulfide ore powder to the micron-sized iron powder is preferably 1:8 to 52, more preferably 1:9 to 18, and most preferably 1: 17.5.
The grinding speed of the ball mill is preferably 500 to 3000rpm, more preferably 500 to 1000 rpm.
The grinding time is preferably 5 to 30 hours.
Specifically, the method of the present invention is preferably carried out by the following steps: mixing elemental sulfur powder or iron sulfide powder or iron pyrite powder with micron-sized iron powder according to the mass ratio of 1: 9-18, placing the obtained mixed raw material into a ball milling tank of a ball mill, wherein the ball milling tank is filled with a grinding medium accounting for 10-50% of the volume of a cavity, the ball milling tank is in an inert gas atmosphere, starting the ball mill, grinding at the speed of 500-1000 rpm for 5-30 hours, and separating the grinding medium from a product after grinding to obtain the iron-ferrous sulfide composite; the micron-sized iron powder is iron powder with the particle size of less than 100 microns; the grinding medium is an iron ball, a steel ball, a silicon nitride ball or a zirconia ball with the diameter of 0.15 mm-10 mm.
The iron-ferrous sulfide complex prepared by the invention can be used for in-situ remediation of chlorine-containing organic pollutants and heavy metals in underground water. The chlorine-containing organic pollutant can be chloroethylene such as chloroethylene, dichloroethylene, trichloroethylene and tetrachloroethylene, chloroethane such as trichloroethane and tetrachloroethane, carbon tetrachloride and the like. The heavy metal can be hexavalent chromium, cadmium ions and the like.
Compared with a chemical synthesis method, the method does not use toxic and harmful chemical raw materials in the preparation process, does not generate waste water or dangerous gas, has low raw material cost, and belongs to an environment-friendly process. The iron-ferrous sulfide complex prepared by the method has high catalytic activity, can be quickly compatible with organic pollutants and continuously degraded, finally is reduced and converted into pollution-free ethane, ethylene and the like, and is very suitable for in-situ remediation of underground water.
(IV) description of the drawings
FIG. 1 is an X-ray diffraction pattern of the iron-ferrous sulfide complex prepared in example 1.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.256g of elemental sulfur powder and 2.244g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:8.76) and placing the elemental sulfur powder and the zero-valent iron powder in a ball milling tank, and filling nitrogen in the ball milling tank; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared iron-ferrous sulfide complex from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 0.5mg L-1, with a 95% degradation rate.
Example 2
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5), continuously stirring and uniformly mixing in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h reaction, the TCE concentration was reduced to 0.9mg L-1, with a degradation rate of 91%.
Example 3
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) filling steel ball grinding beads (with the particle size of 0.8mm) with the volume of 20% of the cavity into a ball grinding tank to serve as grinding media; (2) weighing 0.069g of elemental sulfur powder and 2.43g of zero-valent iron powder (the particle size is 38-74 microns) (the mass ratio of sulfur to iron is 1:35.2) and continuously stirring and mixing uniformly in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, and then a trichloroethylene concentrate was added to control the initial concentration of trichloroethylene to 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 1.2mg L-1, with a degradation rate of 88%.
Example 4
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.047g of elemental sulfur powder and 2.45g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:52.1) and placing the powder in a ball milling tank, and filling nitrogen in the ball milling tank; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 1.6mg L-1, with a degradation rate of 84%.
Example 5
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) filling steel ball grinding beads (with the particle size of 0.6mm) with the volume of 20% of the cavity into a ball grinding tank to serve as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 2 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h reaction, the TCE concentration was reduced to 1.1mg L-1, with a degradation rate of 89%.
Example 6
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the particle size is 6mm) with the volume of 20 percent of the cavity are filled in a ball milling tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5), continuously stirring and uniformly mixing in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 10 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 0.8mg L-1, with a degradation rate of 92%.
Example 7:
the preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the particle size is 1mm) with the volume of 20 percent of the cavity are filled in a ball milling tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5), continuously stirring and uniformly mixing in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 20 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h reaction, the TCE concentration was reduced to 0.4mg L-1, with a degradation rate of 96%.
Example 8
The preparation method of the iron-ferrous sulfide complex by using the sand mill in the laboratory comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.3mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 3000rpm, and grinding for 30 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 0.2mg L-1, with a degradation rate of 98%.
Example 9
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.256g of elemental sulfur powder and 2.244g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:8.76) and placing the elemental sulfur powder and the zero-valent iron powder in a ball milling tank, and filling nitrogen in the ball milling tank; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 20 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
Taking the heavy metal chromium as an example, the activity of the material is examined. A300 mL reagent bottle was filled with 3g of the iron-ferrous sulfide complex, topped with deionized water, capped with a teflon spacer, and then added with a hexavalent chromium stock solution, with the initial concentration of Cr (VI) controlled at 50mg L-1, and the bottle was set on a shaker and shaken. After reacting for 2h, the concentration of Cr (VI) was 2.2mgL-1, and the removal rate was 95.6%.
Example 10
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) iron ball grinding beads (with the particle size of 0.6mm) with the volume of 20 percent of the cavity are filled into a ball grinding tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 20 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
Taking the heavy metal chromium as an example, the activity of the material is examined. A300 mL reagent bottle was filled with 3g of the iron-ferrous sulfide complex, topped with deionized water, capped with a teflon spacer, and then added with a hexavalent chromium stock solution, with the initial concentration of Cr (VI) controlled at 50mg L-1, and the bottle was set on a shaker and shaken. After reacting for 2h, the concentration of Cr (VI) was 3mg L-1, and the removal rate was 94%.
Example 11
The FRITSCH planetary ball mill is strengthened to prepare an iron-ferrous sulfide complex; (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.069g of elemental sulfur powder and 2.43g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:35.2), placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 1000rpm, and grinding for 30 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
Taking the heavy metal chromium as an example, the activity of the material is examined. A300 mL reagent bottle was filled with 3g of the iron-ferrous sulfide complex, topped with deionized water, capped with a teflon spacer, and then added with a hexavalent chromium stock solution, with the initial concentration of Cr (VI) controlled at 50mg L-1, and the bottle was set on a shaker and shaken. After reacting for 2h, the concentration of Cr (VI) was 4mg L-1, and the removal rate was 92%.
Example 12
The FRITSCH planetary ball mill is strengthened to prepare an iron-ferrous sulfide complex; (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.047g of sulfur powder and 2.45g of zero-valent iron powder (the particle size is 38-74 microns) (the mass ratio of sulfur to iron is 1:52.1) and placing the powder in a ball milling tank, and filling nitrogen in the tank; (3) starting the ball mill, adjusting the grinding speed to 1000rpm, and grinding for 30 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
Taking the heavy metal chromium as an example, the activity of the material is examined. A300 mL reagent bottle was filled with 3g of the iron-ferrous sulfide complex, topped with deionized water, capped with a teflon spacer, and then added with a hexavalent chromium stock solution, with the initial concentration of Cr (VI) controlled at 50mg L-1, and the bottle was set on a shaker and shaken. After reacting for 2h, the concentration of Cr (VI) was 5mg L-1, and the removal rate was 90%.
Example 13
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 15 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.256g of elemental sulfur powder and 2.244g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:8.76) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using the heavy metal cadmium as an example. 3g of the iron-ferrous sulfide complex was added to a 300mL reagent bottle, the bottle was filled with deionized water, the bottle was closed with a Teflon spacer, the bottle was then capped with a cap, the cadmium ion stock solution was added, the initial concentration of Cd (II) was controlled to 50mg L-1, and the bottle was set on a shaker and shaken. After 2h of reaction, the concentration of Cd (II) was 4mg L-1, and the removal rate was 92%.
Example 14
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 15 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using the heavy metal cadmium as an example. 3g of the iron-ferrous sulfide complex was added to a 300mL reagent bottle, the bottle was filled with deionized water, the bottle was closed with a Teflon spacer, the bottle was then capped with a cap, the cadmium ion stock solution was added, the initial concentration of Cd (II) was controlled to 50mg L-1, and the bottle was set on a shaker and shaken. After 2h of reaction, the concentration of Cd (II) was 5mg L-1, and the removal rate was 90%.
Example 15
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.069g of elemental sulfur powder and 2.43g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:35.2), placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using the heavy metal cadmium as an example. 3g of the iron-ferrous sulfide complex was added to a 300mL reagent bottle, the bottle was filled with deionized water, the bottle was closed with a Teflon spacer, the bottle was then capped with a cap, the cadmium ion stock solution was added, the initial concentration of Cd (II) was controlled to 50mg L-1, and the bottle was set on a shaker and shaken. After 2 hours of reaction, the concentration of Cd (II) was 5.4mgL-1, and the removal rate was 89.2%.
Example 16
Preparing an iron-ferrous sulfide complex by a laboratory sand mill; (1) silicon nitride ball milling beads (with the particle size of 0.3mm) with the volume of 20 percent of the cavity are filled in a ball milling tank to be used as a grinding medium; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron powder (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the powder in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 2000rpm, and grinding for 10 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using the heavy metal cadmium as an example. 3g of the iron-ferrous sulfide complex was added to a 300mL reagent bottle, the bottle was filled with deionized water, the bottle was closed with a Teflon spacer, the bottle was then capped with a cap, the cadmium ion stock solution was added, the initial concentration of Cd (II) was controlled to 50mg L-1, and the bottle was set on a shaker and shaken. The reagent bottles were monitored periodically for cd (ii) concentration. After 2h of reaction, the concentration of Cd (II) was 3.85mg L-1, and the removal rate was 92.3%.
Example 17
Preparing an iron-ferrous sulfide complex by a laboratory vibration ball mill; (1) zirconia ball grinding beads (the grain diameter is 10mm) with the volume of 20 percent of the cavity are filled in a ball milling tank to be used as grinding media; (2) weighing 0.135g of elemental sulfur powder and 2.365g of zero-valent iron (the particle size is 38-74 micrometers) (the mass ratio of sulfur to iron is 1:17.5) and placing the elemental sulfur powder and the zero-valent iron in a ball milling tank, and filling the tank with nitrogen; (3) starting the ball mill, adjusting the grinding speed to 3000 times/min (about 3000rpm), and grinding for 10 hours; (4) and under the nitrogen atmosphere, separating the prepared particles from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using the heavy metal cadmium as an example. 3g of the iron-ferrous sulfide complex was added to a 300mL reagent bottle, the bottle was filled with deionized water, the bottle was closed with a Teflon spacer, the bottle was then capped with a cap, the cadmium ion stock solution was added, the initial concentration of Cd (II) was controlled to 50mg L-1, and the bottle was set on a shaker and shaken. The reagent bottles were monitored periodically for cd (ii) concentration. After 2h of reaction, the concentration of Cd (II) was 3.88mg L-1, and the removal rate was 92.24%.
Example 18
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.256g of ferrous sulfide powder and 2.244g of zero-valent iron powder (the particle size is 38-74 microns) and placing the ferrous sulfide powder and the 2.244g of zero-valent iron powder in a ball milling tank, and filling nitrogen in the tank; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared iron-ferrous sulfide complex from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 0.6mg L-1, with a degradation rate of 94%.
Example 19
The preparation method of the iron-ferrous sulfide complex by adopting a planetary ball mill comprises the following steps: (1) zirconia ball grinding beads (the grain diameter is 0.6mm) with the volume of 20 percent of the cavity are filled in a ball grinding tank to be used as grinding media; (2) weighing 0.256g of pyrite powder and 2.244g of zero-valent iron powder (the particle size is 38-74 microns) and placing the pyrite powder and the zero-valent iron powder in a ball milling tank, and filling nitrogen in the ball milling tank; (3) starting the ball mill, adjusting the grinding speed to 500rpm, and grinding for 5 hours; (4) and under the nitrogen atmosphere, separating the prepared iron-ferrous sulfide complex from the grinding medium by using a screen to obtain the finished product of the iron-ferrous sulfide complex.
The activity of the above materials was examined using trichloroethylene as an example. A425 mL reagent bottle was filled with 4.25g of the iron-ferrous sulfide complex, topped with deionized water, capped with a Teflon septum, then added with a trichloroethylene concentrate to an initial concentration of 10mg L-1, and the bottle was set on a shaker. After 5h of reaction, the TCE concentration was reduced to 1.2mg L-1, with a degradation rate of 88%.
Claims (10)
1. A preparation method of an iron-ferrous sulfide complex is characterized by comprising the following steps:
the method comprises the following steps of mixing elemental sulfur powder and micron-sized iron powder according to the mass ratio of 1: 8.76-52.1, placing the obtained mixed raw materials into a ball milling tank of a ball milling machine, filling a grinding medium into the ball milling tank, starting the ball milling machine in a vacuum environment or inert gas atmosphere, grinding for 2-30 hours at the grinding speed of 400-4000 rpm, and separating the grinding medium and a product after grinding to obtain the iron-ferrous sulfide composite.
2. The method according to claim 1, wherein the ball mill is a planetary ball mill, a vibration ball mill or a sand mill.
3. The method of claim 1, wherein the micro-sized iron powder is an iron powder having a particle size of less than 100 μm.
4. The method according to claim 1, wherein the grinding medium is an iron ball, a steel ball, a silicon nitride ball, or a zirconia ball having a diameter of 0.15mm to 10 mm.
5. The method of claim 1, wherein the grinding media is loaded in an amount of 10 to 50% by volume of the ball mill pot cavity.
6. The method of claim 1, wherein the inside of the ball mill tank is under an inert gas atmosphere.
7. The preparation method of claim 1, wherein the mass ratio of the elemental sulfur powder to the micron-sized iron powder is 1: 9-18.
8. The method according to claim 1, wherein the grinding time is 5 to 30 hours.
9. The production method according to claim 1, wherein the ball mill has a grinding speed of 500 to 1000 rpm.
10. The preparation method of the iron-ferrous sulfide composite body, according to the mass ratio of the elemental sulfur powder to the micron-sized iron powder of 1: 9-18, placing the obtained mixed raw material into a ball milling tank of a ball milling machine, wherein the ball milling tank is filled with a grinding medium accounting for 10-50% of the volume of a cavity, the ball milling tank is in an inert gas atmosphere, starting the ball milling machine, grinding at the speed of 500-1000 rpm for 5-30 hours, and separating the grinding medium from a product after grinding to obtain the iron-ferrous sulfide composite body; the micron-sized iron powder is iron powder with the particle size of less than 100 microns; the grinding medium is an iron ball, a steel ball, a silicon nitride ball or a zirconia ball with the diameter of 0.15 mm-10 mm.
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| CN102320647A (en) * | 2011-08-17 | 2012-01-18 | 北京科技大学 | Preparation method of copper sulphide nano-powder with different stoichiometric ratios |
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