CN105414554A - Preparation method for iron-ferrous sulfide composite - Google Patents
Preparation method for iron-ferrous sulfide composite Download PDFInfo
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- CN105414554A CN105414554A CN201510753744.5A CN201510753744A CN105414554A CN 105414554 A CN105414554 A CN 105414554A CN 201510753744 A CN201510753744 A CN 201510753744A CN 105414554 A CN105414554 A CN 105414554A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- 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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Abstract
The invention discloses a preparation method for an iron-ferrous sulfide composite. The method comprises the steps that powdered elemental sulfur and micron-grade iron powder are mixed at a mass ratio of 1: 5-60; the obtained mixed raw materials are put into a ball mill tank of a ball mill; the ball mill tank is filled with grinding media, and the ball mill tank is in a vacuum environment or inert gas atmosphere; and the ball mill is started, the grinding speed is 400-4000 rpm, the grinding time is 2-30 hours, the grinding media and a product are separated after grinding, and the iron-ferrous sulfide composite is obtained. The grain size of the prepared iron-ferrous sulfide composite is below 10 micrometers. The preparation method is simple, the raw materials are low in cost, poisonous and harmful dangerous chemicals are not used or generated, and the preparation method achieves the clean production process. The prepared iron-ferrous sulfide composite can efficiently purify chlorine-contained organic pollutants and heavy metals in water, and is especially suitable for in-situ repairing of polluted underground water.
Description
(1) technical field
The present invention relates to the preparation method of a kind of iron-ferrous sulfide complex, is a kind of preparation method of iron-ferrous sulfide complex of high-efficiency environment friendly in particular.
(2) background technology
Zero-valent Iron, as a kind of emerging underground water based technique for in-situ remediation, obtains extensive concern both domestic and external.But Zero-valent Iron also exists many problems in actual application, as ferromagnetism and high surface energy can make it be gathered into bulky grain, and then amount of activated site can not effectively be discharged, the utilization rate of active component is very low; Meanwhile, the ironing surface one deck dense oxidation film of zeroth order can hinder the contact of active component and target contaminant greatly, thus reduces the activity of Zero-valent Iron; In addition, in hydrophilic Zero-valent Iron and solution, hydrophobic organic pollution affinity is not good enough.
In order to overcome above-mentioned simple Zero-valent Iron defect in actual applications, Chinese scholars constantly attempt to Zero-valent Iron modifying surface or and other materials carry out compound.As [Treatmentofchlorinatedorganiccontaminantswithnanoscalebi metallicparticles.Catal.Today.1998 such as Zhang, 40 (4), 387-395.] by after the noble-metal-supporteds to Zero-valent Iron such as platinum, palladium, silver, the speed of Zero-valent Iron degradable organic pollutant improves several times, and catabolite is simpler.Though the noble metals such as platinum, palladium, silver significantly can promote the activity of Zero-valent Iron, cost is higher, and is lost in surrounding medium and very easily causes secondary pollution.
In recent years, ferrous sulfide becomes novel Zero-valent Iron modifier gradually, research finds, the existence of ferrous sulfide can promote degrading activity [the Enhancedreductivedechlorinationoftrichloroethylenebysulf idatednanoscalezerovalentiron.Waterresearch2015 of Zero-valent Iron to pollutant greatly, 78,144-53.; FacileSynthesisandCharacterizationofFe/FeSNanoparticlesf orEnvironmentalApplications.ACSApplMaterInterfaces2011,3 (5), 1457-62.].This is mainly owing to 2 points: the hydrophobicity of (1) ferrous sulfide makes the Zero-valent Iron of ferrous sulfide modification be easier to be combined with organic pollution; (2) ferrous sulfide is semiconductor, and its existence significantly can promote the transmission efficiency of electronics from Zero-valent Iron to target contaminant.Therefore the Zero-valent Iron of ferrous sulfide modification is gathered around in the reparation field of actual polluted-water and is had broad application prospects.But the combination of existing Zero-valent Iron load ferrous sulfide or Zero-valent Iron and ferrous sulfide all adopts chemical method to prepare, preparation method roughly divides two classes: one is first the precursor (ferrous salt) of iron is become Zero-valent Iron by borohydride reduction, then sulfide is added, sulfide can form ferrous sulfide with remaining ferrous ion and be deposited in Zero-valent Iron surface, final formation Zero-valent Iron load ferrous sulfide.Two is add in iron salt solutions by the borohydride solution containing dithionite, forms Zero-valent Iron and ferrous sulfide complex.Though the compound particle of iron prepared by chemical method and ferrous sulfide is less, there is many deficiencies in preparation process: (1) synthetic method is more loaded down with trivial details; (2) in building-up process, iron is very easily oxidized; (3) cost of material is expensive, and can produce a large amount of waste water; (4) boron hydride can produce hydrogen, and building-up process exists certain risk.
(3) summary of the invention
The object of the invention is to overcome the deficiency that existing chemical method prepares iron-ferrous sulfide complex, the physics preparation method of the iron-ferrous sulfide complex providing a kind of preparation technology simple, efficient, clean, safe.
The invention discloses the physical preparation method of a kind of iron-ferrous sulfide complex, this method be simple, efficient, clean, safety, prior art can be efficiently solved and adopt chemical method to prepare the deficiency of iron and ferrous sulfide complex.
The technical solution used in the present invention is:
The preparation method of a kind of iron-ferrous sulfide complex, described method is: elemental sulfur powder and micron order iron powder in mass ratio 1:5 ~ 60 mix, the mixed material obtained is placed in the ball grinder of ball mill, ball grinder, built with abrasive media, is vacuum environment or inert gas atmosphere in ball grinder, opens ball mill, grinding rate 400 ~ 4000rpm, grind 2 ~ 30 hours, after grinding, be separated abrasive media and product, be i.e. obtained described iron-ferrous sulfide complex.
Described micron order iron powder is the iron powder that particle diameter is less than 100 microns, directly can buy on market and obtain.
Ball mill of the present invention can be planetary ball mill, vibrator, sand mill etc.
Described ball grinder is built with abrasive media, and described abrasive media is the iron ball of diameter 0.15mm ~ 10mm, steel ball, silicon nitride ball or zirconia ball, preferential oxidation zirconium ball or silicon nitride ball.
The charge weight of described abrasive media is generally 10 ~ 50% of the cavity volume of ball grinder, and preferably 15% ~ 20%.
Be atmosphere of inert gases or vacuum environment in described ball grinder, preferred atmosphere of inert gases, inert gas can be nitrogen or argon gas.
Be separated abrasive media and product after described grinding, screen cloth can be adopted under inert gas atmosphere to be separated abrasive media and product.
Iron provided by the invention-ferrous sulfide complex is powdery granule, controls granular size by regulating milling time.The particle diameter of the iron that the inventive method obtains-ferrous sulfide composite particle precursor is 50nm ~ 10 μm.
Preferred 1:8 ~ 52 of mass ratio of described elemental sulfur powder and micron order iron powder, more preferably 1:9 ~ 18, most preferably 1:17.5.
The grinding rate preferably 500 ~ 3000rpm of described ball mill, more preferably 500 ~ 1000rpm.
Preferably 5 ~ 30 hours time of described grinding.
Concrete, preferred the inventive method is carried out according to the following steps: elemental sulfur powder and micron order iron powder in mass ratio 1:9 ~ 18 mix, the mixed material obtained is placed in the ball grinder of ball mill, ball grinder built with cavity volume 10 ~ 50% abrasive media, be inert gas atmosphere in ball grinder, unlatching ball mill, grinding rate 500 ~ 1000rpm, grind 5 ~ 30 hours, after grinding, be separated abrasive media and product, be i.e. obtained described iron-ferrous sulfide complex; Described micron order iron powder is the iron powder that particle diameter is less than 100 microns; Described abrasive media is the iron ball of diameter 0.15mm ~ 10mm, steel ball, silicon nitride ball or zirconia ball.
The iron that the present invention obtains-ferrous sulfide complex can be used for contamination with chlorinated organics in in-situ remediation of underground water and heavy metal.Described contamination with chlorinated organics can be chloroethene alkanes and the carbon tetrachloride etc. such as the polyvinyl chloride-bases such as vinyl chloride, dichloroethylene, trichloro-ethylene, tetrachloro-ethylene, trichloroethanes, tetrachloroethanes.Described heavy metal can be chromium, cadmium etc.
Preparation method of the present invention is simple, only needs simple grinding can obtain iron-ferrous sulfide complex, compared to chemical synthesis process, do not use poisonous and harmful chemical raw material in this law preparation process, produce without waste water, produce without hazardous gas, low raw-material cost, belongs to environmentally friendly process.And iron-ferrous sulfide complex catalyzes activity prepared by this law is high, can fast and organic pollution affine, and sustaining degradation, its reduction is converted into free of contamination ethane, ethene etc. the most at last, is highly suitable for underground water in-situ immobilization.
(4) accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum that embodiment 1 prepares iron-ferrous sulfide complex.
(5) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) claim 0.256g elemental sulfur powder and 2.244g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:8.76) to be placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, be separated by obtained iron-ferrous sulfide complex with screen cloth with abrasive media, obtain iron-ferrous sulfide complex finished product, XRD figure as shown in Figure 1.The particle diameter of product is about 100nm ~ 2 μm.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 0.5mgL
-1, degradation rate is 95%.
Embodiment 2
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) Keep agitation mixes in ball grinder to take 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5), and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 0.9mgL
-1, degradation rate is 91%.
Embodiment 3
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the steel ball milling pearl (particle diameter 0.8mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) in ball grinder, Keep agitation mixes, and is full of nitrogen in tank to take 0.069g elemental sulfur powder and 2.43g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:35.2); (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then with adding trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 1.2mgL
-1, degradation rate is 88%.
Embodiment 4
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.047g elemental sulfur powder and 2.45g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:52.1) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 1.6mgL
-1, degradation rate is 84%.
Embodiment 5
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the steel ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 2 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 1.1mgL
-1, degradation rate is 89%.
Embodiment 6
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) Keep agitation mixes in ball grinder to take 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5), and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 10 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 0.8mgL
-1, degradation rate is 92%.
Embodiment 7:
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 1mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) in ball grinder, Keep agitation mixes, and is full of nitrogen in tank to take 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5); (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 20 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 0.4mgL
-1, degradation rate is 96%.
Embodiment 8
Iron-ferrous sulfide complex prepared by laboratory sand mill, and step is as follows: the zirconia ball milling pearl (particle diameter 0.3mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 3000rpm, grinds 30 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For trichloro-ethylene, investigate the activity of above-mentioned material.In 425mL reagent bottle, add 4.25g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add trichloro-ethylene concentrate, the initial concentration controlling trichloro-ethylene is 10mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 5h, the concentration of TCE drops to 0.2mgL
-1, degradation rate is 98%.
Embodiment 9
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) claim 0.256g elemental sulfur powder and 2.244g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:8.76) to be placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 20 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal chromium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, the Cr VI stock solution then added, control Cr (VI) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cr (VI) is 2.2mgL
-1, clearance is 95.6%.
Embodiment 10
Adopt planetary ball mill to prepare iron-ferrous sulfide complex, step is as follows: the iron ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 20 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal chromium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add Cr VI stock solution, control Cr (VI) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cr (VI) is 3mgL
-1, clearance is 94%.
Embodiment 11
FRITSCH planetary ball mill is reinforced, prepares iron-ferrous sulfide complex; (1) the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume is loaded in ball grinder as abrasive media; (2) taking 0.069g elemental sulfur powder and 2.43g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:35.2) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 1000rpm, grinds 30 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal chromium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add Cr VI stock solution, control Cr (VI) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cr (VI) is 4mgL
-1, clearance is 92%.
Embodiment 12
FRITSCH planetary ball mill is reinforced, prepares iron-ferrous sulfide complex; (1) the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume is loaded in ball grinder as abrasive media; (2) taking single 0.047g matter sulphur powder and 2.45g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:52.1) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 1000rpm, grinds 30 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal chromium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add Cr VI stock solution, control Cr (VI) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cr (VI) is 5mgL
-1, clearance is 90%.
Embodiment 13
Adopt planetary ball mill grinding machine to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 15% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.256g elemental sulfur powder and 2.244g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:8.76) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal cadmium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add cadmium ion stock solution, control Cd (II) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cd (II) is 4mgL
-1, clearance is 92%.
Embodiment 14
Adopt planetary ball mill grinding machine to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 15% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinding carries out 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal cadmium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add cadmium ion stock solution, control Cd (II) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cd (II) is 5mgL
-1, clearance is 90%.
Embodiment 15
Adopt planetary ball mill grinding machine to prepare iron-ferrous sulfide complex, step is as follows: the zirconia ball milling pearl (particle diameter 0.6mm) of 20% cavity volume loads in ball grinder as abrasive media by (1); (2) taking 0.069g elemental sulfur powder and 2.43g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:35.2) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 500rpm, grinds 5 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal cadmium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add cadmium ion stock solution, control Cd (II) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.After reaction 2h, the concentration of Cd (II) is 5.4mgL
-1, clearance is 89.2%.
Embodiment 16
Iron-ferrous sulfide complex prepared by laboratory sand mill; (1) the silicon nitride ball milling pearl (particle diameter 0.3mm) of 20% cavity volume is loaded in ball grinder as abrasive media; (2) taking 0.135g elemental sulfur powder and 2.365g zeroth order iron powder (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 2000rpm, grinds 10 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal cadmium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add cadmium ion stock solution, control Cd (II) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.Cd (II) concentration in periodic monitor reagent bottle.After reaction 2h, the concentration of Cd (II) is 3.85mgL
-1, clearance is 92.3%.
Embodiment 17
Iron-ferrous sulfide complex prepared by laboratory vibration ball mill; (1) the zirconia ball milling pearl (particle diameter 10mm) of 20% cavity volume is loaded in ball grinder as abrasive media; (2) taking 0.135g elemental sulfur powder and 2.365g Zero-valent Iron (particle diameter 38 microns ~ 74 microns) (sulphur weight of iron is than being 1:17.5) is placed in ball grinder, and in tank, be full of nitrogen; (3) open ball mill, grinding rate is adjusted to 3000 times/min (being roughly equal to 3000rpm), grinds 10 hours; (4) under nitrogen atmosphere, with screen cloth, obtained particle is separated with abrasive media, obtains iron-ferrous sulfide complex finished product.
For heavy metal cadmium, investigate the activity of above-mentioned material.In 300mL reagent bottle, add 3g iron-ferrous sulfide complex, fill it up with by deionized water, cover tightly with the lid with Teflon partition, then add cadmium ion stock solution, control Cd (II) initial concentration is 50mgL
-1, reagent bottle is put and vibrates on the oscillator.Cd (II) concentration in periodic monitor reagent bottle.After reaction 2h, the concentration of Cd (II) is 3.88mgL
-1, clearance is 92.24%.
Claims (10)
1. the preparation method of iron-ferrous sulfide complex, it is characterized in that described method is: elemental sulfur powder and micron order iron powder in mass ratio 1:5 ~ 60 mix, the mixed material obtained is placed in the ball grinder of ball mill, ball grinder, built with abrasive media, is vacuum environment or inert gas atmosphere in ball grinder, opens ball mill, grinding rate 400 ~ 4000rpm, grind 2 ~ 30 hours, after grinding, be separated abrasive media and product, be i.e. obtained described iron-ferrous sulfide complex.
2. method according to claim 1, is characterized in that described ball mill is planetary ball mill, vibrator or sand mill.
3. method according to claim 1, is characterized in that described micron order iron powder is the iron powder that particle diameter is less than 100 microns.
4. method according to claim 1, is characterized in that described abrasive media is the iron ball of diameter 0.15mm ~ 10mm, steel ball, silicon nitride ball or zirconia ball.
5. method according to claim 1, is characterized in that the charge weight of described abrasive media is 10 ~ 50% of ball grinder cavity volume.
6. method according to claim 1, is characterized in that being inert gas atmosphere in described ball grinder.
7. method according to claim 1, is characterized in that the mass ratio of described elemental sulfur powder and micron order iron powder is 1:9 ~ 18.
8. method according to claim 1, is characterized in that the time of described grinding is 5 ~ 30 hours.
9. method according to claim 1, is characterized in that the grinding rate of described ball mill is 500 ~ 1000rpm.
10. method according to claim 1, it is characterized in that described method is: elemental sulfur powder and micron order iron powder in mass ratio 1:9 ~ 18 mix, the mixed material obtained is placed in the ball grinder of ball mill, ball grinder built with cavity volume 10 ~ 50% abrasive media, be inert gas atmosphere in ball grinder, unlatching ball mill, grinding rate 500 ~ 1000rpm, grind 5 ~ 30 hours, after grinding, be separated abrasive media and product, be i.e. obtained described iron-ferrous sulfide complex; Described micron order iron powder is the iron powder that particle diameter is less than 100 microns; Described abrasive media is the iron ball of diameter 0.15mm ~ 10mm, steel ball, silicon nitride ball or zirconia ball.
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| CN201510753744.5A CN105414554A (en) | 2015-11-06 | 2015-11-06 | Preparation method for iron-ferrous sulfide composite |
| CN201680001438.9A CN106536097B (en) | 2015-11-06 | 2016-04-29 | Preparation method of iron-ferrous sulfide complex |
| PCT/CN2016/080692 WO2017075950A1 (en) | 2015-11-06 | 2016-04-29 | Method for preparing iron-ferrous sulfide composite |
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