CN113070076B - Preparation method and application of zero-valent iron sulfide - Google Patents
Preparation method and application of zero-valent iron sulfide Download PDFInfo
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Abstract
The invention discloses a preparation method and application of zero-valent iron sulfide, wherein the preparation method comprises the following steps: (1) introducing nitrogen into the deionized water to completely remove oxygen in the deionized water to prepare deoxidized water; (2) adding zero-valent iron and a sulfur-containing reagent solution into an infusion bottle containing deoxygenated water, and sealing; (3) putting the sealed infusion bottle into a constant-temperature turner, pre-turning and reacting for a certain time, injecting a trivalent ferric salt solution into the infusion bottle, and continuing turning for a certain time; (4) filtering, freeze drying, sieving, collecting and drying in a drier. The zero-valent iron sulfide prepared by the method can be used for removing heavy metals or chlorine-containing organic matters in wastewater. The preparation method of the vulcanized zero-valent iron can improve the oxidation resistance of the material, reduce the generation of harmful gases and reduce the cost of wastewater treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to a preparation method and application of zero-valent iron sulfide.
Background
At present, with the rapid development of the industries such as electroplating, chemical engineering, mining, metallurgy and the like and the use of a large amount of pesticides, fertilizers and antibiotics, various heavy metals (such as Cr (VI), Cd (II) and the like) and chlorine-containing organic pollutants (such as chloramphenicol) enter the environment through various approaches, so that the physical, chemical, biological and other characteristics of water and soil environment are changed to a certain extent, thereby causing the quality reduction of the water and soil, destroying the ecological environment and harming the human health.
The zero-valent iron has good degradation potential on various heavy metals and halogen-containing organic pollutants due to environmental friendliness, wide sources, strong reducibility and more electron reserves. But the oxide film is easy to oxidize, so that a compact oxide film is generated on the surface, and the continuous reaction of the oxide film is blocked; in addition, the reactivity of the catalyst is sharply reduced along with the increase of the pH, and the pH working range is narrow; also, zero-valent iron is a non-selective reductant that can react with water or other non-target contaminants (e.g., NO)3 -) This greatly contributes to the loss of reducing properties of Zero Valent Iron (ZVI). Therefore, zero-valent iron modification technologies such as acid washing, nano zero-valent iron (nZVI), surface modification stability, loading, heavy metal doping and the like and coupling technologies such as ultrasound, ultraviolet, microwave, weak magnetic fields and the like are carried out, and although the reactivity of the ZVI can be obviously improved by the methods, the electron utilization rate of the ZVI is not fundamentally improved.
In recent years, zero-valent iron and iron sulfide (Fe)xSy) The compound sulfurization technology has attracted much attention because it can better improve the selectivity of ZVI to target pollutants and the utilization rate of electrons. Currently, there are three commonly used vulcanization methods: i) reacting NaBH4With a variety of sulfur sources such as sodium dithionite (Na)2S2O4) Sodium thiosulfate (Na)2S2O3)、Na2S, and the like, and Fe (II) and Fe (III) salt are added in a dropwise manner to produce ferrosulfide (Fe) while preparing zero-valent ironxSy) (ii) a ii) ZVI (nZVI, mZVI) is pretreated by buffering, acid washing, ultrasonic treatment, stirring and the like to generate Fe (II), and then Na is added2S, or directly mixing Fe (II) salt with Na2S is put into a solution containing ZVI to generate FeS which is loaded on the surface of the ZVI; iii) mixing ZVI with elemental sulfur powder, and mechanically ball-milling for 20h under the condition of argon to generate FexSyWith ZVI composites (S-ZVI).
The sulfuration method mainly focuses on the generation of FeS on the surface of ZVI, but is easy to generate more toxic and harmful gas H in the wet sulfuration process2S, air pollution and potential safety hazard are caused; meanwhile, dry vulcanization requires a long-time anaerobic environment (such as nitrogen or argon filling) due to spontaneous combustion of sulfur powder, and thus the cost is high. In addition, the surface of the zero-valent iron sulfide with FeS as the main sulfur phase is easy to oxidize and has poor stability, so that the storage and treatment cost is increased. Therefore, a new zero-valent iron vulcanization preparation process needs to be explored urgently, the reactivity of the material can be ensured, the emission of harmful gas can be reduced, and the cost is reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of zero-valent iron sulfide, so as to achieve the purposes of reducing harmful gas generation, improving the oxidation resistance of materials and reducing the cost.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of zero-valent iron sulfide comprises the following steps:
(1) introducing nitrogen into the deionized water to completely remove oxygen in the deionized water to prepare deoxidized water;
(2) adding zero-valent iron and a sulfur-containing reagent solution into an infusion bottle containing deoxygenated water, and sealing; wherein, the sulfur-containing reagent is added firstly to destroy the surface oxide film (oxide or oxyhydroxide containing Fe (III)) of zero-valent iron (ZVI) to generate a small amount of FeS and FeS2。
2Fe3++3S2-→FeS2+FeS；
(3) Putting the sealed infusion bottle into a constant-temperature turner, turning over in advance for reaction for a certain time to ensure that the vulcanizing reagent firstly destroys an oxide layer and part of S2-After adsorbing to the surface of zero-valent iron (ZVI), injecting a ferric salt solution into the infusion bottle, and continuously turning over for a certain time;
(4) filtering, freeze drying, sieving, collecting and drying in a drier.
Equations that may occur for this process are:
2Fe3++S2-→2Fe2++S0
2Fe3++2S2-→FeS2+Fe2+
2Fe3++Fe0→3Fe2+
Fe2++S2-→FeS
FeS+S0→FeS2
in the scheme, in the step (1), the volume of the deionized water is 100-500mL, the flow rate of the introduced nitrogen is 0.1-1.5mL/min, and the time of introducing the nitrogen is 10-60 min.
In the scheme, in the step (2), the zero-valent iron is micron-sized zero-valent iron powder, the particle size is 50-500 meshes, and the amount of the zero-valent iron is 0.5-5 g.
In the scheme, in the step (2), the sulfur-containing reagent is Na2S、K2S6、Na2S2O4、Na2S2O3The concentration of the sulfur reagent solution is 0.2-5mol/L, and the molar ratio of the sulfur reagent to zero-valent iron is 0.014-0.224.
In the scheme, in the step (3), the temperature of the constant temperature reactor is controlled to be 20-35 ℃, the revolution of the constant temperature reactor is controlled to be 60-200rpm, the pre-overturning time is 5-30min, and the overturning time is continued to be 360-1440min after the trivalent iron salt solution is added.
In the above scheme, in the step (3), the ferric salt is FeCl3、Fe(NO3)3The concentration of the ferric salt solution is 0.2-5mol/L, and the molar ratio of the sulfur-containing reagent to the ferric salt is 1:0.5-1: 6.
In the scheme, in the step (4), the filtration membrane for suction filtration is an organic filtration membrane with the diameter of 0.22-1.0 μm, the freeze drying time is 2-6h, the filtration membrane is sieved by a 100-200-mesh sieve, the nitrogen content in the dryer is 80-95%, and the humidity content in the dryer is 2-10%.
The application of the zero-valent iron sulfide prepared by the preparation method in removing heavy metals or chlorine-containing organic matters in wastewater.
In a further technical scheme, the dosage of the zero-valent iron sulfide is 0.1-0.8g/L, the pH of the wastewater is 3-10, and electrolytes contained in the wastewater are sodium sulfate, sodium chloride, acetic acid-sodium acetate buffer and MES biological buffer.
In a further technical scheme, the oxygen content in the wastewater is 0-10mg/L, the turning or stirring revolution required in the wastewater treatment process is 90-400rpm, the required temperature is 20-30 ℃, and the hydraulic retention time of the zero-valent iron sulfide in the wastewater is 1-3 hours.
Through the technical scheme, the preparation method and the application of the zero-valent iron sulfide provided by the invention have the following beneficial effects:
1. the reactivity of the zero-valent iron sulfide prepared by the invention is obviously better than that of the existing FeS and ZVI composite-based material, the pollutant removal efficiency is higher, and the application prospect of the zero-valent iron is widened.
2. The invention selects Fe (III) rather than Fe (II) salt, which can greatly inhibit H in the preparation process of the material2And S is generated, so that the cleaning and the safety are better.
3. The prepared vulcanized zero-valent iron has good oxidation resistance and still has good reactivity after being placed for a long time.
4. The zero-valent iron sulfide prepared by the method has better treatment capacity on heavy metals or chlorine-containing organic pollutants, and can activate H2O2And persulfate catalyzes advanced oxidation to degrade pollutants, and has better universality in the field of treatment of environmental pollutants.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an XRD representation of zero-valent iron sulfide materials prepared in example 1 and comparative example 1 of the present invention;
FIG. 2 is an XPS characterization chart of the zero-valent iron sulfide materials prepared in example 1 and comparative example 1 of the present invention;
FIG. 3 is a kinetic curve of the zero-valent iron sulfide material prepared in example 1 and comparative examples 1 and 2 of the present invention for treating wastewater containing Cr (VI) heavy metals;
FIG. 4 shows the treatment of wastewater containing Cr (VI) heavy metals with the material obtained in example 1 of the present invention on different days of aging;
FIG. 5 is a kinetic curve of the zero-valent iron sulfide material prepared in example 1 and comparative examples 3 and 4 of the present invention for treating wastewater containing Cr (VI) heavy metals;
FIG. 6 is a comparison of the removal of Chloramphenicol (CAP) under aerobic conditions for the zero-valent iron sulfide materials prepared in example 1 and comparative example 3 of the present invention;
FIG. 7 shows the catalysis of Persulfate (PMS) and hydrogen peroxide (H) by the zero-valent iron sulfide material prepared in example 1 of the invention2O2) Profile of degradation of Chloramphenicol (CAP) in the system.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a preparation method of vulcanized zero-valent iron, which comprises the following steps:
example 1:
250mL of deionized water is put into an infusion bottle and is communicated with N2For 30min to completely deoxygenate. Then, 1g of 200 mesh micron Zero Valent Iron (ZVI) was added and 2mL of 1mol/L Na was added at the desired S/Fe molar ratio (0.112)2And (5) turning and shaking the S solution for 10 min. Then, the molar ratio (S) is given2-:Fe3+1:2) 4mL of 1mol/L FeCl was added3Controlling the conditions of a turnover oscillator at 25 ℃ and 120rpm, carrying out turnover oscillation for 720min, carrying out suction filtration through a 0.45-micron organic filter membrane, freeze-drying for 3h, sieving with a 200-mesh sieve, collecting, and placing in a dryer, wherein the material is marked as S0@ZVI。
The preparation method has no odor of egg, i.e. no H2S, the filtration membrane is not blocked by suction filtration and is easy to separate.
Comparative example 1
250mL of deionized water is put into an infusion bottle and is communicated with N2For 30min to completely deoxygenate. Then, 10mL of 1mol/L Na was added thereto2After the solution is dissolved, the molar ratio (S) is calculated2-:Fe3+1:2) 20mL of 1mol/L FeCl was added3Controlling the conditions of a turnover shaker at 25 deg.C and 120rpm, shaking for 720min, centrifuging at 1000g and 4 deg.C, freeze drying for 10 hr, collecting, and drying in a drier0 syn。
Comparative example 2
64mg of S prepared as described above0 synMixing with 1g ZVI at S/Fe 0.112 to obtain S0 syn+ZVI。
Comparative example 3
Using the reaction of example 1 with S0The same preparation procedure of @ ZVI, in which only FeCl is added3Replacement by FeSO4And the molar ratio S2-:Fe2+1:1, prepared to give FeS @ ZVI.
Comparative example 4
Using the reaction of example 1 with S0The same preparation procedure as for @ ZVI, except that Na is added2Replacement of S solution by Na2S2，FeCl3Replacement by FeSO4And the molar ratio S2 2-:Fe2+1:1 to give FeS2@ZVI。
For S obtained in example 10@ ZVI S from comparative example 10 synAnd purchased analytically pure sulfur powder (S)0 com) XRD and XPS characterization were performed, and the results are shown in FIGS. 1 and 2. Na (Na)2S and FeCl3The solution is mixed according to the molar ratio (S)2-:Fe3+1:2) addition, material S prepared in comparative example 10 synWith the purchased analytically pure sulfur powder (S)0 com) The XRD results were consistent. And press S2-:Fe3+Preparation of S1: 20@ ZVI a small S appears at 23 ° 2 θ0Diffraction peaks, junction characterized by XPS at the same timeThe fruits also showed a surface S predominantly consisting of S0The form exists.
The invention also provides an application of the zero-valent iron sulfide, which comprises the following steps:
1. s from example 1 was used0@ ZVI S from comparative example 10 synS obtained in comparative example 20 syn+ ZVI, analytical pure Sulfur powder purchased (S)0 com) And micron zero-valent iron (ZVI), and treating wastewater containing heavy metal Cr (VI) under an anoxic condition.
250mL of acetic acid-sodium acetate buffer solution is added into a 250mL reaction bottle, the pH value is controlled between 5.5 and 6.5, and 1mL of 5mg/mL Cr (VI) stock solution is added to prepare the artificially synthesized Cr (VI) wastewater with the concentration of 20 mg/L. 1.5mL of sample was taken, and 0.1g of micron zero-valent iron (ZVI) and purchased elemental sulfur powder (S) were added0 com) Elemental sulfur powder (S) synthesized in comparative example 10 syn) S prepared by directly mixing elemental sulfur powder synthesized in comparative example 2 with ZVI0 syn+ ZVI and S synthesized in example 10@ZVI(S/Fe＝0.112)。
The reaction flask was placed in an inverted shaker at 25 ℃ at 120rpm for reaction. The results are shown in FIG. 3, S within 60min0@ ZVI, 100% of Cr (VI) can be completely removed, while ZVI and S0 com、S0 synAnd S0 syn+ ZVI removes only 1.5%, 3.3%, 17.3% and 47.8% of Cr (VI) at 120min, respectively. As can be seen, S was prepared in comparative example 20Then directly mixed with ZVI to strengthen the removal of Cr (VI) from ZVI, while the embodiment 1 of the invention generates S0While allowing it to complex with ZVI0@ ZVI is more capable of significantly enhancing the removal of Cr (VI) by ZVI, and the reaction rate is about 10 times that of the direct mixing of the two in comparative example 2.
2. Using the material S prepared in example 10@ ZVI the wastewater containing the heavy metal Cr (VI) is treated under anoxic conditions, without aging and after 30 days of aging in air, respectively.
Adding 250mL acetic acid-sodium acetate buffer solution into 250mL reaction bottle, controlling pH to 5.5-6.5, adding 1mL Cr (VI) stock solution of 5mg/mLPreparing the artificially synthesized Cr (VI) wastewater with the concentration of 20 mg/L. 1.5mL of sample was taken, and 0.1g S was added to each sample0@ ZVI (S/Fe ═ 0.084) non-aged material and material aged in air for 30 days were reacted in a reaction flask placed in an inverted shaker at 120rpm and 25 ℃. The results are shown in FIG. 4, S after 30 days of aging0The @ ZVI material can still remove 98.3 percent of Cr (VI) within 120min, and has better oxidation resistance and applicability.
3. Material S prepared in comparative example 10@ ZVI, commercially available micro Zero Valent Iron (ZVI), FeS @ ZVI as obtained in comparative example 3, and FeS as obtained in comparative example 42@ ZVI, the performance of the treatment of heavy metals Cr (VI) respectively under anoxic conditions.
250mL of acetic acid-sodium acetate buffer solution is added into a 250mL reaction bottle, the pH value is controlled to be between 5.5 and 6.5, and 1mL of 5mg/mL Cr (VI) stock solution is added to prepare the synthetic Cr (VI) wastewater with the concentration of 20 mg/L. 1.5mL of sample was taken, and 0.1g of ZVI and S were added to the sample0@ ZVI, FeS @ ZVI and FeS2@ ZVI (S/Fe ═ 0.112), and the reaction flask was placed in an inverted shaker at 25 ℃ and 120 rpm. The results are shown in FIG. 5, S0The @ ZVI material can remove 100 percent of Cr (VI) within 60min, and the performance is far higher than that of FeS @ ZVI and FeS2@ ZVI, which removed only 19.9% and 30.1% of Cr (VI), respectively, in 120 min. In addition, for pseudo first order rate constants, S prepared by the method0@ ZVI is FeS @ ZVI and FeS in the present study, respectively239 times and 22 times of @ ZVI, from which it can be seen that S is present in the vulcanization process of the invention0The effect of removing Cr (VI) by the strengthened zero-valent iron is far higher than that of removing FeS and FeS in the prior research2Is a vulcanization method of the main body.
4. Using the material S obtained in example 10@ ZVI and FeS @ ZVI, a material prepared in comparative example 3, were compared for their effect on removal of the chlorinated organic contaminant Chloramphenicol (CAP) under aerobic conditions to illustrate S0The application potential and superiority of @ ZVI in the aspect of organic pollutant removal.
500mL of ultrapure water, 2mM Na2SO4Electrolyte, 40mg/L CAP, without adjusting pH, 0.2g/L ZVI, S0@ ZVI and FeS @ ZVI (S/Fe ═ 0.084), mechanically stirred at 350rpm andthe reaction is carried out for 180min by controlling the temperature of the water bath (T ═ 25 ℃). FIG. 6 shows that ZVI and S are present within 180min0@ ZVI and FeS @ ZVI remove 11.3%, 46.1% and 70.1% chloramphenicol, respectively, at pseudo first order rates of 0.0005, 0.0067 and 0.0034min-1. Therefore, compared with the ZVI, the effect of removing chloramphenicol by the sulfuration zero-valent iron prepared by the method is 13.4 times higher than that of the FeS @ ZVI in the current research, and the strengthening effect of the sulfuration zero-valent iron is 6.8 times higher than that of the zero-valent iron. Thus S prepared by the vulcanization method0The @ ZVI also has good application potential in the field of organic matter removal.
5. The material S in example 1 was used0@ ZVI and purchased micron Zero Valent Iron (ZVI), catalytically activating Peroxymonosulfate (PMS) and hydrogen peroxide (H) under aerobic conditions2O2) Degrading chloramphenicol and verifying the application potential of the material in the aspect of degrading pollutants by advanced oxidation technology.
500mL of ultrapure water, 40mg/L of Chloramphenicol (CAP), and an appropriate amount of an oxidizing agent (0.307g of PMS or 50. mu. L H)2O2) 2mM Na is added into a PMS system2SO4The pH was not adjusted, and after 10min of reaction, 0.1g/L of ZVI and S were added0@ ZVI (S/Fe ═ 0.084), stirred mechanically at 350rpm and the temperature controlled in a water bath (T ═ 25 ℃), reacted for 180 min. As shown in FIG. 7, in the PMS system, ZVI and S0The removal rates of @ ZVI on chloramphenicol were 28.2% and 94.5% within 180min, respectively, and the pseudo first order rate results also show S0The reaction performance of @ ZVI is 10 times that of ZVI; at H2O2Under the system, the two can respectively remove 15.0 percent and 94.4 percent of chloramphenicol and S0@ ZVI performance is 27 times higher than ZVI. It can be seen that S prepared by the vulcanization process of the present invention0The @ ZVI has greater application potential in advanced oxidation processes.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the zero-valent iron sulfide is characterized by comprising the following steps of:
(1) introducing nitrogen into the deionized water to completely remove oxygen in the deionized water to prepare deoxidized water;
(2) adding zero-valent iron and a sulfur-containing reagent solution into an infusion bottle containing deoxygenated water, and sealing;
(3) putting the sealed infusion bottle into a constant-temperature turner, pre-turning and reacting for a certain time, injecting a trivalent ferric salt solution into the infusion bottle, and continuing turning for a certain time;
(4) filtering, freeze drying, sieving, collecting and drying in a drier.
2. The method as claimed in claim 1, wherein in step (1), the volume of deionized water is 100-500mL, the flow rate of nitrogen is 0.1-1.5mL/min, and the time of nitrogen introduction is 10-60 min.
3. The method for preparing zero-valent iron sulfide of claim 2, wherein in the step (2), the zero-valent iron is micron-sized zero-valent iron powder with a particle size of 50-500 meshes and the amount of the zero-valent iron is 0.5-5 g.
4. The method for preparing zero-valent iron sulfide of claim 1, wherein in step (2), the sulfur-containing reagent is Na2S、K2S6、Na2S2O4、Na2S2O3The concentration of the sulfur reagent solution is 0.2-5mol/L, and the molar ratio of the sulfur reagent to zero-valent iron is 0.014-0.224.
5. The method as claimed in claim 1, wherein in the step (3), the temperature of the isothermal reactor is controlled to be 20-35 ℃, the rotation speed of the isothermal reactor is controlled to be 60-200rpm, the pre-tumbling time is 5-30min, and the tumbling time is continued to be 360-1440min after the ferric salt solution is added.
6. The method for preparing zero-valent iron sulfide of claim 1, wherein in the step (3), the ferric salt is FeCl3、Fe(NO3)3The concentration of the ferric salt solution is 0.2-5mol/L, and the molar ratio of the sulfur-containing reagent to the ferric salt is 1:0.5-1: 6.
7. The method as claimed in claim 1, wherein in the step (4), the filtration membrane for filtration is an organic filtration membrane with a diameter of 0.22-1.0 μm, the freeze-drying time is 2-6h, the filtration membrane is 100-200 mesh, the content of nitrogen in the dryer is 80-95%, and the humidity in the dryer is 2-10%.
8. Use of the zero-valent iron sulfide prepared by the preparation method of claim 1 in removing heavy metals or chlorine-containing organic matters in wastewater.
9. The use of claim 8, wherein the zero valent iron sulfide is added in an amount of 0.1 to 0.8g/L, the pH of the wastewater is 3 to 10, and the electrolyte contained in the wastewater is sodium sulfate, sodium chloride, acetic acid-sodium acetate buffer, MES biological buffer.
10. The use according to claim 8, wherein the oxygen content in the wastewater is 0-10mg/L, the required number of tumbling or stirring revolutions during the treatment of the wastewater is 90-400rpm, the required temperature is 20-30 ℃, and the hydraulic retention time of the zero-valent iron sulfide in the wastewater is 1-3 hours.
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| CN114259975B (en) * | 2021-12-28 | 2022-12-02 | 华中科技大学 | Modified zero-valent iron and preparation method and application thereof |
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| CN114799199B (en) * | 2022-04-19 | 2024-02-02 | 浙江大学 | Sulfur content and morphology controllable vulcanized nano zero-valent iron and preparation method and application thereof |
| CN115254938B (en) * | 2022-08-08 | 2023-11-21 | 大连理工大学 | Method for efficiently activating persulfate to degrade organic pollutants by reducing sulfur to regulate iron-based material |
| CN115432828A (en) * | 2022-08-26 | 2022-12-06 | 曜昂环境技术(江苏)有限公司 | In-situ reduction remediation agent for chlorinated organic compounds in soil groundwater |
| CN116550341A (en) * | 2023-05-12 | 2023-08-08 | 浙江工业大学 | Preparation method and application of zero-valent iron sulfide based on iron mud of water purification plant |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101190287B1 (en) * | 2012-03-08 | 2012-10-12 | 포항공과대학교 산학협력단 | Synthesis of nano-ferrous iron coated with iron sulfide sediment on the surface by hydrogen sulfide ion and method for purifying polluted soil and groundwater environmental pollutants |
| CN104291435A (en) * | 2014-11-03 | 2015-01-21 | 济南大学 | Method of treating organic waste water by adopting Fe/FeS composite material activated dioxygen |
| CN105174414A (en) * | 2015-09-28 | 2015-12-23 | 中国地质大学（武汉） | FeS and Fe0 composite and preparation method and application thereof |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
| CN106396074A (en) * | 2016-09-30 | 2017-02-15 | 浙江工业大学 | Fast organic pollutant removing method based on vulcanized zero-valence-iron-activated hydrogen peroxide |
| CN107032474A (en) * | 2017-06-06 | 2017-08-11 | 山东大学深圳研究院 | A kind of method of alta-mud load sulfide modifier nanometer iron composite material processing waste water containing chrome under magnetic fields |
| CN107081125A (en) * | 2017-06-06 | 2017-08-22 | 山东大学深圳研究院 | A kind of vulcanization nanometer zero-valent iron composite material of alta-mud load and preparation method and application |
| CN108856275A (en) * | 2018-07-03 | 2018-11-23 | 南京万德斯环保科技股份有限公司 | A kind of method of repairing polluted soil and Organic Chemicals In Groundwater |
| CN110369708A (en) * | 2019-07-26 | 2019-10-25 | 山东大学 | A kind of method that aging is modified the preparation method of Zero-valent Iron and is modified Zero-valent Iron degradating chloro organic pollutant using aging |
| CN111392844A (en) * | 2020-02-18 | 2020-07-10 | 山东大学 | Method and system for accelerating removal of Cr (VI) in water body by using zero-valent iron sulfide based on surface functional group regulation |
| CN112028131A (en) * | 2020-06-16 | 2020-12-04 | 暨南大学 | Vulcanized nano zero-valent iron and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150001157A1 (en) * | 2013-06-26 | 2015-01-01 | Corning Incorporated | Methods and apparatus for multi-part treatment of liquids containing contaminants using zero valent nanoparticles |
| CN104492461A (en) * | 2014-12-11 | 2015-04-08 | 同济大学 | Preparation method and application of nano-silica introduced magnetic vulcanized nanometer zero-valent iron |
| CN104827028B (en) * | 2015-04-15 | 2016-04-20 | 刘骁勇 | Composite nano zero-valent iron particle |
| US20170297931A1 (en) * | 2016-04-13 | 2017-10-19 | The Royal Institution For The Advancement Of Learning/Mcgill University | Sulfidated nanoscale zerovalent iron and method of use thereof |
| CN110627187B (en) * | 2019-08-30 | 2021-07-09 | 山东大学 | Preparation method and application of vulcanization modified zero-valent iron composite material |
-
2021
- 2021-02-25 CN CN202110211274.5A patent/CN113070076B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101190287B1 (en) * | 2012-03-08 | 2012-10-12 | 포항공과대학교 산학협력단 | Synthesis of nano-ferrous iron coated with iron sulfide sediment on the surface by hydrogen sulfide ion and method for purifying polluted soil and groundwater environmental pollutants |
| WO2013133509A1 (en) * | 2012-03-08 | 2013-09-12 | 효림산업주식회사 | Synthesis of nanoscale zero valent iron coated with iron sulfide precipitate on surface thereof by means of hydrogen sulfide ions and method for purifying environmental pollutants in contaminated soil and ground water using same |
| CN104291435A (en) * | 2014-11-03 | 2015-01-21 | 济南大学 | Method of treating organic waste water by adopting Fe/FeS composite material activated dioxygen |
| CN105174414A (en) * | 2015-09-28 | 2015-12-23 | 中国地质大学（武汉） | FeS and Fe0 composite and preparation method and application thereof |
| CN105859015A (en) * | 2016-05-27 | 2016-08-17 | 山东大学 | Method for removing orange yellow I in printing and dyeing wastewater by using sulfurized modified zero-valent iron material under effect of low-intensity magnetic field |
| CN106396074A (en) * | 2016-09-30 | 2017-02-15 | 浙江工业大学 | Fast organic pollutant removing method based on vulcanized zero-valence-iron-activated hydrogen peroxide |
| CN107032474A (en) * | 2017-06-06 | 2017-08-11 | 山东大学深圳研究院 | A kind of method of alta-mud load sulfide modifier nanometer iron composite material processing waste water containing chrome under magnetic fields |
| CN107081125A (en) * | 2017-06-06 | 2017-08-22 | 山东大学深圳研究院 | A kind of vulcanization nanometer zero-valent iron composite material of alta-mud load and preparation method and application |
| CN108856275A (en) * | 2018-07-03 | 2018-11-23 | 南京万德斯环保科技股份有限公司 | A kind of method of repairing polluted soil and Organic Chemicals In Groundwater |
| CN110369708A (en) * | 2019-07-26 | 2019-10-25 | 山东大学 | A kind of method that aging is modified the preparation method of Zero-valent Iron and is modified Zero-valent Iron degradating chloro organic pollutant using aging |
| CN111392844A (en) * | 2020-02-18 | 2020-07-10 | 山东大学 | Method and system for accelerating removal of Cr (VI) in water body by using zero-valent iron sulfide based on surface functional group regulation |
| CN112028131A (en) * | 2020-06-16 | 2020-12-04 | 暨南大学 | Vulcanized nano zero-valent iron and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Core-Shell Fe/FeS Nanoparticles with Controlled Shell Thickness for Enhanced Trichloroethylene Removal";Brumovsky, M et al.;《ACS Appl. Mater. Interfaces》;20200708;第12卷(第31期);第35425页右栏第2.1-2.2节 * |
| "硫化微米零价铁去除水中氯霉素的性能与机理研究";杨晓薇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20201115(第11期);正文第16-17页第2.2节，第27页4.1.1节及28页图4.1、4.1.2节，第31页4.1.5节 * |
| Brumovsky, M et al.."Core-Shell Fe/FeS Nanoparticles with Controlled Shell Thickness for Enhanced Trichloroethylene Removal".《ACS Appl. Mater. Interfaces》.2020,第12卷(第31期),第35424-35434页. * |
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