CN115475951A - Silicate-loaded micro-nano zero-valent iron sulfide with core-shell structure and preparation method and application thereof - Google Patents
Silicate-loaded micro-nano zero-valent iron sulfide with core-shell structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicate supported micro-nano zero-valent iron sulfide with a core-shell structure and a preparation method and application thereof, belonging to the technical field of resource comprehensive utilization and environmental chemistry. The method comprises the steps of grinding and uniformly mixing iron ore, a reducing agent and a vulcanizing agent, adding water to prepare carbon-containing pellets, drying the carbon-containing pellets, and then carrying out reduction roasting at 850-1200 ℃ to obtain the silicate supported micro-nano zero-valent iron sulfide material with the core-shell structure, wherein the material has the function of efficiently treating printing and dyeing wastewater and heavy metal wastewater. The method for preparing the micro-nano zero-valent iron sulfide material by using the cheap iron ore has the advantages of simple process flow, low production cost, environmental friendliness, high product added value and the like.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of mineral resources and environmental chemistry, in particular to a silicate supported micro-nano zero-valent iron sulfide with a core-shell structure and a preparation method and application thereof.
Background
As a water treatment agent which is cheap and easy to obtain, environment-friendly and strong in reduction performance, the zero-valent iron (ZVI) can remove various pollutants in water, such as heavy metals, halogenated organic matters, nitro compounds, azo dyes and the like, through oxidation, reduction and adsorption coprecipitation. Based on the above, the zero-valent iron plays an important role in the fields of groundwater in-situ remediation, industrial wastewater treatment, drinking water purification and the like. However, in practical engineering, the zero-valent iron is easily oxidized and passivated, so that the defects of poor pollutant removal reactivity, low target pollutant Electron Selectivity (ES) and the like are gradually exposed, which limits the wide application of the zero-valent iron to a certain extent. Therefore, how to synchronously improve the decontamination reaction activity and the electron selectivity of zero-valent iron has become a hot research focus in recent years.
In recent years, zero-valent iron and iron sulfide (Fe) 1-x S) the compound sulfuration technology is widely concerned because the selectivity of zero-valent iron to target pollutants and the electron utilization rate can be better improved. Currently, there are three commonly used vulcanization methods: i) Reacting NaBH 4 With a variety of sulfur sources such as sodium dithionite (Na) 2 S 2 O 4 ) Sodium thiosulfate (Na) 2 S 2 O 3 )、Na 2 S, etc. are mixed, and Fe (II) and Fe (III) salt are dropped to produce ferrosulfide (Fe) while preparing zero-valent iron 1-x S); II) the zero-valent iron (nZVI, mZVI) is pretreated by buffering, acid washing, ultrasonic treatment, stirring and the like to generate Fe (II), and then Na is added 2 S, or directly mixing Fe (II) salt with Na 2 S is put into a solution containing zero-valent iron to generate FeS which is loaded to zeroA surface of iron values; iii) Mixing zero-valent iron and elemental sulfur powder, and mechanically ball-milling for 20h under the condition of argon to generate Fe 1-x S and zero-valent iron composite material (vulcanized zero-valent iron).
The invention patent application with the application publication number of CN104492461A discloses a preparation method of nano-silicon dioxide induced magnetic vulcanized nano zero-valent iron, which comprises the following specific steps: (1) Adding sodium borohydride and sodium persulfate into water to form a mixed solution; (2) Adding nano silicon dioxide into a solution containing sodium borohydride and sodium persulfate, and continuously stirring; (3) Slowly dripping the suspension formed in the step (2) into an iron salt solution through a peristaltic pump under the stirring condition; (4) After the reaction is finished, performing solid-liquid separation by using a magnet, respectively washing twice by using water and absolute ethyl alcohol, and finally directly storing in a water-ethanol solution or storing in an anaerobic glove box after vacuum drying. The method belongs to a liquid phase reduction method, the used raw materials are expensive (especially sodium borohydride), the process is complex, and toxic and harmful gases (H) can be generated in the reaction process 2 S,H 2 ) Therefore, no large-scale industrial application has been reported at present.
The invention patent ZL202110913606.4 discloses a preparation method of sulfurated zero-valent iron, which comprises the steps of mixing zero-valent iron powder and Na 2 And S is mixed according to the molar ratio of 2-10. In addition, researchers have reported that micron-sized zero-valent iron sulfide is synthesized by a mechanical ball milling method using zero-valent iron (400 mesh) and elemental sulfur as raw materials (Gu, Y.; wang, B.; he, F.; bradley, M.J.; tratnyek, P.G. mechanochemical Sulfated microscopical zero valve irone, pathways, kinetics, mechanism, and efficiency of trichloroethylene depletion. Envir on. Sci. Technol.2017,51 (21), 12653-12662). The two methods belong to a mechanical ball milling method, the zero-valent iron sulfide prepared by the method can overcome the defect of high cost of raw materials, and micron-sized materials are convenient to transport and store and are easier to apply in practice. However, the preparation method has high requirements on equipment, consumes a large amount of energy and increases the preparation cost.
In addition, the invention patent ZL201710223275.5 discloses a preparation method of vulcanized zero-valent iron, which comprises the following specific steps: (1) Introducing nitrogen into the water to completely remove oxygen in the 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 process is simpler than the liquid phase reduction process, does not use expensive borohydride, but uses commercial zero-valent iron and sulfur-containing reagents as raw materials, thereby increasing the production cost.
The problems of high raw material price, complex process, high production cost and difficult large-scale production exist in the preparation of the zero-valent iron sulfide by adopting a liquid phase reduction method or a mechanical ball milling method or other existing methods. Therefore, it is necessary to explore a new method for preparing zero-valent iron sulfide to solve the above technical problems.
Disclosure of Invention
Based on the above reasons, the present invention aims to provide a silicate supported micro/nano zero-valent iron sulfide with a core-shell structure, a preparation method and an application thereof, which solve or at least partially solve the technical defects in the prior art. The method for preparing the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure can improve the oxidation resistance of materials, realize large-scale generation and reduce the cost.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of silicate supported micro-nano zero-valent iron sulfide with a core-shell structure specifically comprises the following steps:
(1) Grinding ore: grinding and uniformly mixing iron ore, a vulcanizing agent and a carbonaceous reducing agent according to a certain proportion to obtain mixed powder;
(2) Preparing the iron ore sulfur-containing and carbon-containing pellets: adding water into the mixed powder obtained in the step (1), and then pelletizing or pressing to obtain the iron ore sulfur-containing carbon-containing pellets;
(3) Reduction roasting: and (3) drying the sulfur-containing and carbon-containing pellets of the iron ore obtained in the step (2), then reducing and roasting for 15-100 min at 850-1200 ℃, and after roasting and sintering, cooling the obtained product under the condition of isolating oxygen to obtain the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure.
Further, in the technical scheme, the size of the iron ore in the step (1) is preferably less than or equal to 1mm.
Further, according to the technical scheme, the content of Fe in the iron ore in the step (1) is more than 30%, and is preferably 35-50%. If the Fe content in the iron ore is too low, the generated zero-valent iron sulfide is too small in amount and is easily wrapped by silicate minerals, and the effect is not good when the iron ore is subsequently applied to treating pollutants; if the Fe content in the iron ore is too high, siO 2 If the content is too low, the particle size of the generated zero-valent iron sulfide particles is large, and the effect of the zero-valent iron sulfide on treating pollutants is also influenced. SiO 15% in iron ore 2 Less than or equal to 30 percent, caO less than or equal to 5 percent and MgO less than or equal to 2 percent, if the content of the alkaline ore is too high, siO is generated 2 And the catalyst is easy to react with alkaline oxides to generate molten silicate, so that the zero-valent iron sulfide particles are agglomerated and wrapped by the silicate, and the pollutant treatment performance of the catalyst is influenced.
Further, according to the technical scheme, the iron ore in the step (1) is any one or combination of limonite, hematite and magnetite.
Further, in the above technical solution, the vulcanizing agent in step (1) is any one or a combination of more of sulfur, sodium sulfide, pyrite, ferrous sulfide, and sodium sulfate.
Further, in the above technical solution, the carbonaceous reducing agent in step (1) is any one or a combination of more of anthracite, bituminous coal, lignite, and the like, and is preferably anthracite.
Further, according to the technical scheme, the mass ratio of the iron ore, the vulcanizing agent and the carbonaceous reducing agent in the step (1) is 100: s: (20 to 40), wherein: s is more than or equal to 0 and less than or equal to 20. If the iron ore or carbonaceous reducing agent contains sufficient S element, the addition of the sulfidizing agent is not necessary.
Further, according to the technical scheme, the adding amount of the water in the step (2) is 8-10% of the mass of the iron ore.
Further, in the above technical scheme, the drying process of the sulfur-containing and carbon-containing pellets of iron ore in the step (3) specifically comprises: the carbon-containing pellets are dehydrated and dried for 0.5 to 2 hours at the temperature of between 100 and 120 ℃.
Specifically, in the technical scheme, the reduction roasting in the step (3) aims to generate the zero-valent iron sulfide, and the roasted product is cooled under the condition of oxygen isolation to obtain the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure.
The second purpose of the invention is to provide the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure, which is prepared by the method.
Further, according to the technical scheme, the vulcanized zero-valent iron is in a core-shell structure, and the outer-layer structure component is Fe 1-x S (wherein x =0 to 0.2); the core structure mainly comprises Fe and contains a small amount of S, and the closer to the sphere center, the lower the S content.
Further, according to the technical scheme, the granularity of the vulcanized zero-valent iron is 100 nm-5 microns, and the vulcanized zero-valent iron is distributed on the surface of the loose silicate mineral.
The third purpose of the invention is to provide the application of the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure prepared by the method in removing heavy metal ions in wastewater or degrading organic dyes in wastewater.
The reaction mechanism involved in the present invention is as follows:
iron minerals in the iron ore are reduced to zero-valent iron by CO generated by gasification of a carbonaceous reducing agent, and other gangue minerals react with a loose silicate matrix and serve as carriers for sulfuration of the zero-valent iron. When sulfur is used as a vulcanizing agent, sulfur steam is generated by the gasification of elemental sulfur, and the sulfur steam reacts with zero-valent iron generated by the reduction of iron ore to generate vulcanized zero-valent iron and covers the surface of the zero-valent iron; when ferrous sulfide is used as a vulcanizing agent, the ferrous sulfide reacts with zero-valent iron to generate vulcanized zero-valent iron, and the iron-sulfur compound has a low melting point and is easy to cover the surface of the zero-valent iron to form the vulcanized zero-valent iron; when sodium sulfide is used as a sulfur source, under a high-temperature reducing atmosphere, the sodium sulfide and zero-valent iron are combined to form zero-valent iron sulfide and cover the surface of the zero-valent iron. When sodium sulfate is used as a sulfur source, the sodium sulfate is decomposed to generate sodium sulfide under a high-temperature reducing atmosphere, and the sodium sulfide is combined with zero-valent iron to form zero-valent iron sulfide and covers the surface of the zero-valent iron.
Compared with the prior art, the invention has the following beneficial effects:
the method utilizes the cheap iron ore to prepare the micro-nano zero-valent iron sulfide material, and has the advantages of wide raw material source, simple process flow, low production cost, environmental friendliness, high product added value and the like; the prepared zero-valent iron sulfide material has the function of efficiently treating printing and dyeing wastewater and heavy metal wastewater, has strong oxidation resistance and can realize large-scale application. The obtained vulcanized zero-valent iron is in a core-shell structure, and the outer layer is Fe 1-x S, the inner core is mainly Fe, the inner layer also contains a small amount of S, and the closer to the center of the sphere, the lower the S content. Outer layer Fe 1-x S can not only increase the specific surface area of iron particles and accelerate the reaction rate with pollutants, but also protect the inner iron from reacting with oxygen in the air and improve the oxidation resistance of the material. In the treatment of pollutants, fe 1-x S has hydrophobicity, can react with pollutants preferentially, can accelerate the electron transfer rate when reacting with the pollutants, and can effectively improve the utilization rate of zero-valent iron. The loose silicate matrix is used as a carrier of the vulcanized zero-valent iron particles, so that the vulcanized zero-valent iron particles can be prevented from being agglomerated in the wastewater treatment process to reduce activity, and the long-term high-efficiency decontamination capability is ensured.
Drawings
FIG. 1 is a process flow chart of the process for preparing micro-nano zero-valent iron sulfide from iron ore;
fig. 2 is an XRD chart of the micro-nano zero-valent iron sulfide prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a cross section of a zero-valent iron sulfide material prepared in example 1 of the present invention.
FIG. 4 is a SEM image of a cross section of zero-valent iron sulfide prepared in example 1 of the present invention and an EDS elemental distribution diagram;
FIG. 5 is a graph comparing the degradation effects of three products prepared in comparative example 1 (without using a vulcanizing agent), comparative example 2 (with sulfur as a vulcanizing agent), and example 1 (with pyrite as a vulcanizing agent) for degrading dye wastewater (methyl orange), respectively;
FIG. 6 is a graph comparing the degradation effect of the products prepared in example 1 and comparative example 3 for degrading methyl orange on day 0 and day 30, respectively.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific operations will be given to illustrate the invention, but the scope of the present invention is not limited to the following embodiments.
The equipment and raw materials used in the present invention are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
The multi-element analysis of a limonite, broken to-1 mm before use, is shown in Table 1. The sulfidizing agent used was pyrite, the multielement analysis of which is shown in table 2, crushed to-1 mm before use. The carbonaceous reducing agent was anthracite, and the coal quality analysis is shown in table 3, and it was crushed to-1 mm before use.
TABLE 1 Multi-element analysis of limonite
| Element(s) | Fe | SiO 2 | MgO | Al 2 O 3 | K 2 O |
| Content (%) | 43.11 | 17.39 | 0.94 | 0.75 | 0.13 |
| Element(s) | CaO | Pb | Cu | Zn | Mn |
| Content (%) | 1.19 | 0.03 | 0.12 | 0.06 | 0.25 |
TABLE 2 Multi-element analysis of pyrite
| Element(s) | Fe | S | SiO 2 | Al 2 O 3 | K 2 O |
| Content (%) | 45.41 | 52.10 | 0.90 | 0.49 | 0.03 |
| Element(s) | CaO | Mn | / | / | / |
| Content (%) | 0.029 | 0.019 | / | / | / |
TABLE 3 Industrial analysis results of anthracite
The method for preparing silicate supported micro-nano zero-valent iron sulfide with a core-shell structure by using iron ore specifically comprises the following steps:
mixing limonite, pyrite and anthracite according to the mass ratio of 100:6:20, uniformly mixing for 60min at the speed of 300r/min by using a planetary mill, taking out, and adding 8% of water for uniformly mixing. Preparing the mixed material into carbon-containing pellets on a double-roller ball press, and drying the carbon-containing pellets at 105 ℃. And (3) putting the carbon-containing pellets into a muffle furnace, heating to 1000 ℃, then preserving heat for 1h, taking out after roasting, isolating oxygen at room temperature, cooling, grinding and screening to-100 meshes to obtain the silicate-supported micro-nano zero-valent iron sulfide material with the core-shell structure.
FIG. 2 is an XRD (X-ray diffraction) pattern of the micro-nano zero-valent iron sulfide prepared in the embodiment 1, and as can be seen from FIG. 2, the roasted product of the material mainly comprises Fe, gamma-Fe and SiO 2 、Fe 1-x S and other phases.
FIG. 3 is a cross-sectional view of the zero-valent iron sulfide prepared in example 1 of the present invention, the particles of the zero-valent iron sulfide are relatively uniform, the particle size distribution is 100 nm-5 μm, and the zero-valent iron sulfide particles are uniformly loaded on the surface of the loose silicate mineral without agglomeration.
FIG. 4 is a sectional SEM image and an EDS elemental analysis image of the zero-valent iron sulfide prepared in example 1 of the present invention, and it can be seen from the images that the zero-valent iron sulfide has a typical core-shell structure, the core is zero-valent iron, and the outer layer is Fe 1-x And S, gradually reducing the S content from the outside to the inside.
The micro-nano zero-valent iron sulfide material prepared in the embodiment 1 of the invention is applied to treat chromium-containing wastewater, wherein Cr is Cr 6+ Adjusting the pH value of the wastewater to about 3 when the concentration is 960mg/L, adding 10g/L of zero-valent iron sulfide material, mechanically stirring (200 r/min) for reaction for 40min 6+ The removal rate was 95%.
Example 2
Multielement analysis of a hematite is shown in table 4, crushed to-1 mm before use. The vulcanizing agent is a mixture of sodium sulfate and ferrous sulfide. The carbonaceous reducing agent was a mixture of bituminous coal, lignite and anthracite, and the coal quality analysis was as shown in tables 5 and 6, respectively, and crushed to-1 mm before use.
TABLE 4 Multi-element analysis of hematite
| Element(s) | Fe | SiO 2 | MgO | Al 2 O 3 | K 2 O |
| Content (%) | 35.24 | 25.67 | 1.75 | 1.05 | 0.24 |
| Element(s) | CaO | TiO 2 | Zn | Mn | S |
| Content (%) | 3.49 | 0.35 | 0.13 | 0.06 | 0.06 |
TABLE 5 Industrial analysis results of bituminous coal
Table 6 industrial analysis results of brown coal
The method for preparing silicate supported micro-nano zero-valent iron sulfide with a core-shell structure by using iron ore specifically comprises the following steps:
hematite: vulcanizing agent (sodium sulfate: ferrous sulfide mass ratio 3:7): the carbonaceous reducing agent (lignite: anthracite: bituminous coal mass ratio of 3: 10:30, uniformly mixing for 60min at the speed of 250r/min by using a planetary mill, taking out, and adding 8% of water for uniformly mixing. And then pelletizing. And drying the wet ball at 105 ℃, then putting the wet ball into a graphite dry pot, roasting the wet ball in a muffle furnace at a preset temperature of 850 ℃ for 100min, and then taking out the wet ball to isolate oxygen and cooling the wet ball to room temperature. Grinding and screening to-100 meshes to obtain the silicate loaded micro-nano zero-valent iron sulfide with the core-shell structure.
The micro-nano zero-valent iron sulfide material prepared in the embodiment 2 of the invention is used for treating certain nickel-containing wastewater, wherein Ni is Ni 2+ Adjusting the pH value of the wastewater to about 6 at a concentration of 330mg/L, adding 6g/L micro-nano zero-valent iron sulfide material, mechanically stirring (250 r/min) for reaction for 50min 2+ The removal rate was 97%.
Example 3
The multi-element analysis of a certain magnetite is shown in Table 7, and the multi-element analysis results of limonite and hematite are shown in tables 1 and 4, respectively, and are crushed to-1 mm before use. The vulcanizing agent is a mixture of sodium sulfate and ferrous sulfide. The carbonaceous reducing agent was a mixture of bituminous coal, lignite and anthracite, and the coal quality analysis was as shown in tables 3, 5 and 6, respectively, and was crushed to-1 mm before use.
TABLE 7 multielement analysis of magnetite
| Element(s) | Fe | SiO 2 | MgO | Al 2 O 3 | K 2 O |
| Content (%) | 40.21 | 28.32 | 0.42 | 3.01 | 0.32 |
| Element(s) | CaO | S | Cu | Zn | Mn |
| Content (%) | 1.43 | 0.10 | 0.06 | 0.05 | 0.03 |
The method for preparing silicate supported micro-nano zero-valent iron sulfide with a core-shell structure by using iron ore specifically comprises the following steps:
iron ore (magnetite: limonite: hematite mass ratio 4: a vulcanizing agent (sodium sulfide: sulfur: pyrite mass ratio 3: bituminous coal is prepared from 100 mass percent: 3:40, uniformly mixing for 60min at the speed of 250r/min by using a planetary mill, taking out, adding 8% of water, uniformly mixing, and then pelletizing. And drying the wet balls at 105 ℃, putting the dried wet balls into a graphite dry pot, then putting the graphite dry pot into a muffle furnace with preset 1050 ℃ for roasting for 40min, and then taking out the graphite dry pot, isolating oxygen and cooling to room temperature. Grinding and screening to-100 meshes to obtain the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure.
The micro-nano zero-valent iron sulfide material prepared in the embodiment 3 of the invention is applied to treating certain printing and dyeing wastewater, the COD is 3390mg/L, and the chroma is about 900 times. Adjusting the pH value of the wastewater to be neutral, adding 20g/L of a zero-valent iron sulfide material, and reacting for 70min by mechanical stirring (250 r/min), wherein the COD removal rate is 71 percent, and the chroma removal rate is 98 percent.
Even if the micro-nano zero-valent iron sulfide material prepared in the embodiment 3 of the invention is placed in the air for one month and then used for treating certain printing and dyeing wastewater, the COD is 3390mg/L, and the chroma is about 900 times. Adjusting the pH value of the wastewater to be neutral, adding 20g/L of a zero-valent iron sulfide material, and reacting for 70min by mechanical stirring (250 r/min), wherein the COD removal rate is 68 percent and the chroma removal rate is 96 percent. The same waste water is treated under the same condition, the vulcanized zero-valent iron prepared by the method has obvious antioxidant effect, and the decontamination performance is kept basically stable.
Comparative example 1
A material of this comparative example was prepared essentially the same as example 1 except that: the raw materials adopted by the comparative example are limonite and anthracite, no vulcanizing agent is adopted, and other preparation processes are the same.
Comparative example 2
A material of this comparative example was prepared essentially the same as example 1 except that: the vulcanizing agent adopted in the comparative example is elemental sulfur, and the ratio of limonite: sulfur: anthracite coal is mixed according to the mass ratio of 100:3.2:25 the other preparation processes are the same.
The three materials prepared in comparative example 1 (without vulcanizing agent), comparative example 2 (with sulfur as vulcanizing agent) and example 1 (with pyrite as vulcanizing agent) were used for treating a 500mg/L methyl orange wastewater solution, the material usage amount was 2.5g/L, the solution pH was neutral, and the experiment was repeated 3 times, and the results are shown in FIG. 5. From the results of fig. 5, it is clear that the removal rate of methyl orange after 60min of reaction without adding a vulcanizing agent of zero-valent iron is only 9.89%, while the removal rates of methyl orange by the zero-valent iron sulfide prepared by adding 6% of pyrite and 3.2% of sulfur are 70.07% and 91.11%, respectively.
Comparative example 3
The comparative example is a porous silicate supported micro-nano iron sulfide copper alloy material prepared by using copper slag as a raw material, and the multi-element analysis result of the copper slag is shown in table 8.
TABLE 8 multielement analysis of copper slags
| Element(s) | Fe | SiO 2 | MgO | Al 2 O 3 | K 2 O |
| Content (%) | 39.23 | 30.64 | 0.32 | 4.12 | 0.35 |
| Element(s) | CaO | S | Cu | TiO 2 | Na 2 O |
| Content (%) | 5.43 | 0.76 | 1.47 | 0.32 | 0.39 |
The preparation method for producing the porous silicate supported micro-nano iron sulfide copper alloy by using the copper slag comprises the following steps:
copper slag: anthracite coal: sodium carboxymethylcellulose: the pyrite is prepared from 100:25:0.5:6 weighing and mixing, then adding 8% of water and mixing evenly. Preparing the mixed material into carbon-containing pellets on a double-roller ball press, and drying the carbon-containing pellets at 105 ℃. And (3) putting the carbon-containing pellets into an atmosphere furnace, charging nitrogen for protection, heating to 1000 ℃, then preserving heat for 60min, and cooling along with the furnace under the nitrogen protection after roasting is finished to obtain the porous silicate supported micro-nano iron sulfide copper alloy.
The materials prepared by using copper slag in comparative example 3 and limonite in example 1 were respectively used for treating 500mg/L of methyl orange wastewater solution, the material dosage is 2.5g/L, the solution pH is neutral, the experiment is repeated for 3 times, and the iron-copper sulfide alloy prepared by comparative example 3 and the zero-valent iron sulfide material prepared by example 1 are placed in the air for one month and then used for treating the methyl orange wastewater solution, and other experimental conditions are unchanged, and the result is shown in FIG. 6. As can be seen from fig. 6, the removal rate of methyl orange by the iron sulfide copper alloy prepared by using the copper slag of comparative example 3 as a raw material was only 13.13% after the reaction for 60 min. After the material is placed in the air for one month, the removal rate of methyl orange is reduced to 7.15 percent; while the removal rate of the methyl orange by the zero-valent iron sulfide prepared by taking the limonite in example 1 as the raw material is 95.40%, and the removal rate of the methyl orange is still 90.11% after the material is placed in the air for one month.
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. A preparation method of silicate supported micro-nano zero-valent iron sulfide with a core-shell structure is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) Grinding ore: grinding and uniformly mixing iron ore, a vulcanizing agent and a carbonaceous reducing agent according to a certain proportion to obtain mixed powder;
(2) Preparing the sulfur-containing and carbon-containing pellets of the iron ore: adding water into the mixed powder obtained in the step (1), and then pelletizing or pressing to obtain the iron ore sulfur-containing carbon-containing pellets;
(3) Reduction roasting: and (3) drying the sulfur-containing and carbon-containing pellets of the iron ore obtained in the step (2), then reducing and roasting for 15-100 min at 850-1200 ℃, and after roasting and sintering, cooling the obtained product under the condition of isolating oxygen to obtain the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure.
2. The method of claim 1, wherein: in the step (1), the iron content in the iron ore is more than 30%, and SiO in the iron ore is more than or equal to 15% 2 ≤30％，CaO≤5％，MgO≤2％。
3. The method of claim 1, wherein: the iron ore in the step (1) is any one or combination of limonite, hematite and magnetite.
4. The method of claim 1, wherein: the vulcanizing agent in the step (1) is any one or combination of more of sulfur, sodium sulfide, pyrite, ferrous sulfide and sodium sulfate.
5. The method of claim 1, wherein: the carbonaceous reducing agent in the step (1) is any one or combination of more of anthracite, bituminous coal and lignite.
6. The method of claim 1, wherein: in the step (1), the mass ratio of the iron ore to the vulcanizing agent to the carbonaceous reducing agent is 100: s: (20 to 40), wherein: s is more than or equal to 0 and less than or equal to 20.
7. The silicate supported micro-nano zero-valent iron sulfide with the core-shell structure prepared by the method of any one of claims 1 to 6.
8. The silicate supported micro-nano zero-valent iron sulfide with the core-shell structure according to claim 7, wherein the silicate supported micro-nano zero-valent iron comprises: the vulcanized zero-valent iron is in a core-shell structure, and the component of the outer-layer structure is Fe 1-x S; the core structure component is mainly Fe and contains a small amount of S, and the closer to the sphere center, the lower the S content is; wherein: x =0 to 0.2.
9. The micro-nano zero-valent iron sulfide of claim 7, wherein: the granularity of the vulcanized zero-valent iron is 100 nm-5 mu m, and the vulcanized zero-valent iron is distributed on the surface of the loose silicate mineral.
10. The application of the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure prepared by the method of any one of claims 1 to 6 or the silicate supported micro-nano zero-valent iron sulfide with the core-shell structure of any one of claims 7 to 9 in removing heavy metal ions in wastewater or degrading organic dyes in wastewater.
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