CN112645426B - Modified nano ferrous sulfide composite material and preparation method and application thereof - Google Patents
Modified nano ferrous sulfide composite material and preparation method and application thereof Download PDFInfo
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- CN112645426B CN112645426B CN202110106190.5A CN202110106190A CN112645426B CN 112645426 B CN112645426 B CN 112645426B CN 202110106190 A CN202110106190 A CN 202110106190A CN 112645426 B CN112645426 B CN 112645426B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention relates to the technical field of water treatment, in particular to a modified nano ferrous sulfide composite material and a preparation method and application thereof. The modified nano ferrous sulfide composite material comprises sericin and nano ferrous sulfide. According to the invention, sericin is bonded on the surface of the nano ferrous sulfide, so that electrostatic repulsion and steric hindrance among nano ferrous sulfide particles are increased, and agglomeration among the nano ferrous sulfide particles can be further inhibited. And the formed composite material has obviously reduced sedimentation rate, and obviously improved oxidation resistance and migration capacity in a saturated porous medium. And sericin and nano ferrous sulfide can realize the synergistic removal of heavy metals in sewage.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a modified nano ferrous sulfide composite material and a preparation method and application thereof.
Background
With the rapid development of modern industry, the environmental pollution of underground water is increasingly serious. Among them, organic and heavy metal pollutants in the urban retired industrial land have strong biological toxicity, and if proper restoration and treatment are not added, the reuse process of the retired land is influenced, and the human health and ecological safety can be directly harmed. The pollutant repairing technology mainly comprises an ex-situ repairing technology and an in-situ repairing technology, wherein in the pollutant repairing process, the repairing of an underground aquifer is most challenging, the ex-situ repairing technology has the defects of high cost and low efficiency, and the in-situ repairing technology has the problems of being influenced by factors such as slow mass transfer rate, low reaction efficiency and the like and great difficulty. Therefore, the development of a green, efficient and economical remediation technology for polluted underground aquifers is urgently needed.
Nano ferrous sulfide (FeS) has been widely used in environmental remediation and hazardous waste treatment as a very promising engineering nano remediation material. FeS is a high-efficiency reducing agent, and Fe (II) and S (-II) can be used As electron donors, so that FeS has a good treatment effect on common pollutants in soil and underground water, such As Hg, Cr (VI), As and the like. However, due to the factors of large van der waals force, high surface energy, large density and the like, the exposed FeS is easy to agglomerate and deactivate, so that the exposed FeS is trapped in a porous medium due to deposition in the migration process, and the migration of the exposed FeS is hindered. And the naked FeS nano-particles with low chemical reaction activity are difficult to disperse in underground aquifer media, so that the effect of the FeS nano-particles in environmental remediation is limited. Therefore, FeS nanoparticles must be modified to increase their stability, mobility and reactivity.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the bare FeS nano-particles with low chemical reaction activity in the prior art are difficult to disperse in an underground aquifer medium and limit the effect of the bare FeS nano-particles in environmental remediation, thereby providing a modified nano ferrous sulfide composite material and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a modified nano ferrous sulfide composite material, which comprises sericin and nano ferrous sulfide.
Optionally, the carboxyl functional group of the sericin is bonded on the surface of the ferrous sulfide particle in a form of bidentate bridging.
Optionally, in the composite material, the molar ratio of the sericin to the nano ferrous sulfide is (0.0001-0.005) in terms of ferrous ions: 1.
the invention also provides a method for preparing the modified nano ferrous sulfide composite material in any one of the schemes, which comprises the following steps:
dispersing sericin in water under an anaerobic condition to form a suspension, then adding a ferrous salt aqueous solution into the suspension, uniformly mixing, dropwise adding a sulfide salt aqueous solution, reacting, standing, and drying to obtain the composite material.
Optionally, the sericin is dispersed in water at 30-60 ℃ to form a suspension.
Optionally, the aqueous ferrous salt solution comprises (NH)4)2Fe(SO4)2·6H2O、FeSO4·7H2O and FeCl2·5H2At least one of O; and/or the presence of a gas in the gas,
the sulfide salt comprises Na2S·9H2O、Na2S2O4And CH3CSNH2At least one of (1).
Optionally, the molar ratio of the ferrous salt to the sulfide salt is (1.2-1): 1.
optionally, the preparation method further comprises a step of performing solid-liquid separation after standing.
Optionally, the drying step is to dry a solid phase obtained by solid-liquid separation.
Optionally, the drying comprises at least one of vacuum drying, freeze drying, vacuum freeze drying.
The invention also provides application of the modified nano ferrous sulfide composite material in treatment of heavy metal-containing wastewater.
The invention also provides application of the modified nano ferrous sulfide composite material in-situ remediation of heavy metal polluted groundwater.
The technical scheme of the invention has the following advantages:
1. the sericin of the modified nano ferrous sulfide composite material provided by the invention is a natural polymer based on protein extracted from silkworm cocoons, the molecular weight of the sericin is between 10 and 400kDa, the sericin is composed of 18 amino acids, and most of the sericin has rich functional groups such as hydroxyl, carboxyl and amino. Sericin is a byproduct in the silk degumming process, and has the characteristics of hydrophilicity, amphipathy, oxidation resistance, antibiosis, no toxicity and the like. According to the invention, sericin is bonded on the surface of the nano ferrous sulfide, so that electrostatic repulsion and steric hindrance among nano ferrous sulfide particles are increased, and agglomeration among the nano ferrous sulfide particles can be further inhibited. And the formed composite material has obviously reduced sedimentation rate, and obviously improved oxidation resistance and migration capacity in a saturated porous medium. In addition, sericin also has adsorption performance, so that sericin and nano ferrous sulfide in the formed composite material can realize the synergistic removal of heavy metals in sewage.
2. According to the modified nano ferrous sulfide composite material provided by the invention, sericin is a byproduct in a silk degumming process, and is usually discharged in a large amount in wastewater.
3. The modified nano ferrous sulfide composite material provided by the invention can enhance the dispersion capacity and migration performance of the composite material by adjusting the molar ratio of sericin to ferrous salt. When the molar ratio of sericin to dimethyl salt is (0.0001-0.005): 1, the composite material has good dispersion effect and high migration performance.
4. The method for preparing the modified nano ferrous sulfide composite material is simple, convenient and efficient, and the composite material is quickly synthesized in a coprecipitation mode, so that the preparation period is short, the cost is low, and the effect is good.
5. The modified nano ferrous sulfide composite material provided by the invention is applied to treatment of wastewater containing heavy metals, has the characteristics of good dispersion effect and high migration performance, can effectively remove the heavy metals in the wastewater, and has high removal efficiency.
6. The modified nano ferrous sulfide composite material has the characteristics of good dispersion effect and high migration performance, can effectively remove heavy metals in sewage, and has high removal efficiency.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an infrared spectrum of sericin modified nano ferrous sulfide provided in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of nano-ferrous sulfide in Experimental example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the modified nano ferrous sulfide composite material in test example 1 of the present invention;
FIG. 4 is a transmission electron micrograph of nano-ferrous sulfide in Experimental example 1 of the present invention;
FIG. 5 is a transmission electron microscope image of the modified nano ferrous sulfide composite material in test example 1 of the present invention;
FIG. 6 is a graph showing the penetration of modified nano-ferrous sulfide composite provided by each example of Experimental example 2 of the present invention and nano-ferrous sulfide provided by comparative example 1 in a saturated porous medium;
FIG. 7 is a graph showing the effect of the modified nano ferrous sulfide composite material provided in each example of Experimental example 3 of the present invention and the effect of nano ferrous sulfide and sericin provided in comparative example 1 on the removal of Cr (VI);
FIG. 8 is a graph comparing the stability of the modified nano-ferrous sulfide composite provided by each of the examples of Experimental example 4 of the present invention and the nano-ferrous sulfide provided by comparative example 1;
FIG. 9 is a graph showing the change in the soluble Fe (II) concentration of the modified nano-ferrous sulfide composite provided in each of the experimental examples 5 of the present invention and the nano-ferrous sulfide provided in comparative example 1;
fig. 10 is a graph showing changes in redox potentials of the modified nano-ferrous sulfide composite material provided in each example of experimental example 5 of the present invention and the nano-ferrous sulfide provided in comparative example 1.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The invention provides a modified nano ferrous sulfide composite material, which comprises sericin and nano ferrous sulfide.
Optionally, the carboxyl functional group of the sericin is bonded on the surface of the ferrous sulfide particle in a form of bidentate bridging.
Optionally, in the composite material, the molar ratio of sericin to nano ferrous sulfide is (0.0001-0.005) calculated by ferric ions: 1.
the invention also provides a method for preparing the modified nano ferrous sulfide composite material in any one of the schemes, which comprises the following steps:
dispersing sericin in water under an anaerobic condition to form a suspension, then adding a ferrous salt aqueous solution into the suspension, uniformly mixing, dropwise adding a sulfide salt aqueous solution, reacting, standing, and drying to obtain the composite material.
Alternatively, the oxygen-free conditions may be under conditions which are inert, such as in N2The preparation of the composite material is carried out in the environment, and the oxygen-free condition is limited to avoid the oxidative deterioration caused by the reaction of ferrous salt and oxygen.
It is noted that the water and the aqueous solution added in the preparation process are both subjected to deoxidation treatment, and the deoxidation treatment can adopt N2Is carried out, all operations are carried out at N2The protection is carried out, so that the ferrous salt can be prevented from being oxidized and deteriorated due to the reaction with dissolved oxygen in water.
Optionally, the inert atmosphere is N2。
Optionally, the sericin is dispersed in water at 30-60 ℃ to form a suspension. At the temperature, sericin can be quickly dissolved, and the denaturation of sericin due to overhigh temperature can be avoided.
Optionally, the aqueous ferrous salt solution comprises (NH)4)2Fe(SO4)2·6H2O、FeSO4·7H2O and FeCl2·5H2At least one of O; and/or the presence of a gas in the gas,
the sulfide salt comprises Na2S·9H2O、Na2S2O4CH3CSNH2At least one of (1).
Optionally, the molar ratio of the ferrous salt to the sulfide salt is (1.2-1): 1.
optionally, the standing time is 6-12 h. The standing time is mainly defined to allow better crystallization of the product.
Optionally, the preparation method further comprises a step of performing solid-liquid separation after standing.
Optionally, the solid-liquid separation includes at least one of vacuum filtration and centrifugation.
Optionally, the drying step is to dry a solid phase obtained by solid-liquid separation.
Optionally, the drying comprises at least one of vacuum drying, freeze drying, vacuum freeze drying.
The invention also provides application of the modified nano ferrous sulfide composite material in treatment of heavy metal-containing wastewater.
The invention also provides application of the modified nano ferrous sulfide composite material in-situ remediation of heavy metal polluted groundwater.
Sericin involved in the examples was purchased from saint biotechnology limited of sanshan country.
Example 1
The embodiment relates to a modified nano ferrous sulfide composite material, wherein the molar ratio of sericin to ferrous sulfide in the composite material is 0.001:1 in terms of ferrous ions, and the composite material is prepared according to the following steps:
s1, water deoxidation treatment: 500mL of Wahaha pure water was placed in a beaker, and N was continuously added2And (5) removing dissolved oxygen in the water for 1 h.
S2, solution preparation: preparing a 1% sericin solution by using the deoxidized pure water obtained in the step S1, and diluting 20mL of 1% sericin solution to 100 mL;
preparing a 0.0228M ferrous sulfate solution by using the deoxidized pure water obtained in the step S1;
preparing a 0.0228M sodium sulfide solution using the deoxygenated pure water obtained in step S1;
s3 at N2Under the protection of (3), adding 50mL of prepared ferrous chloride solution into the sericin solution obtained in the step S2;
s4 at N2Under the protection of (3), 50mL of prepared sodium sulfide solution is added dropwise into the mixed system obtained in the step S3;
s5 at N2Under the protection of (3), fully reacting and standing for 24 hours to obtain 500mg/L of the sericin-ferrous sulfide composite material, centrifuging, and carrying out vacuum freeze drying on the obtained solid phase to obtain the sericin modified ferrous sulfide composite material.
Infrared spectrum detection is carried out on the sericin modified ferrous sulfide composite material to represent the structure: according to the positive and negative carboxyl wave number difference delta v of sericin (SS) in an infrared spectrogramSericinThe difference delta between the positive and negative carboxyl wavenumbers of the modified FeS nano material in an infrared spectrogramνModified FeSThe relationship between them determines the adsorption configuration: if the infrared spectrogram has a C-O characteristic peak and delta vModified FeS>ΔνSericinThen the adsorption configuration belongs to monoatomic chelation; if the infrared spectrogram has no C-O characteristic peak and is delta vModified FeS<ΔνSericinThen the adsorption configuration belongs to bidentate chelation; if the infrared spectrogram has no C-O characteristic peak and is delta vModified FeS≈ΔνSericinThe adsorption configuration then belongs to a bidentate bridge.
The infrared spectrogram of the unmodified ferrous sulfide nanomaterial, sericin and the modified ferrous sulfide nanomaterial in the embodiment is shown in fig. 1.
According to FIG. 1, there is no C-O characteristic peak (1720 cm)-1)，ΔνModified FeS(183cm-1)≈ΔνSericin(190cm-1) The sericin is shown to be bound to the surface of the FeS particle in the form of carboxyl groups bridged via double teeth.
Examples 2 to 5
Examples 2-5 relate to a modified nano ferrous sulfide composite material, and examples 2-5 differ from example 1 only in that in examples 2-5, the molar ratio of sericin to ferrous sulfide in the composite material is 0.0001, 0.0005, 0.002, 0.005, respectively, in terms of ferrous ions.
Comparative example 1
The comparative example relates to a nano ferrous sulfide prepared according to the following steps:
s1, mixing 0.316g of FeSO4·7H2Dissolving O in 50mL of oxygen-free deionized water to obtain 0.023 mol.L-1FeSO of (2)4·7H2O solution;
s2, mixing 0.273g of Na2S·9H2Dissolving O in 50mL of oxygen-free deionized water to obtain 0.023 mol.L-1Na of (2)2S·9H2O solution;
s3, in a glove box (95% N)2+5％H2) In (1), 0.023 mol.L-1FeSO of (2)4·7H2The O solutions were added to 100mL of deoxygenated water, and 0.023 mol.L was added-1N of (A)a2S·9H2Adding O solution into the system drop by drop, standing for 24h to obtain 500 mg.L-1Modified FeS stock solution of (a). And after standing, separating the solution on a centrifugal machine, and washing the separated substances for multiple times to obtain the unmodified FeS nano material.
Test example 1
The nano ferrous sulfide provided in comparative example 1 and the modified nano ferrous sulfide composite material provided in example 1 were scanned by using a scanning electron microscope and a transmission electron microscope, and the morphological characteristics, particle size and dispersibility of the two were observed.
The scanning results are shown in fig. 2-5, wherein fig. 2 is a scanning electron microscope image of nano ferrous sulfide, fig. 4 is a transmission electron microscope image of nano ferrous sulfide, fig. 3 is a scanning electron microscope image of modified nano ferrous sulfide composite material, and fig. 5 is a transmission electron microscope image of modified nano ferrous sulfide composite material, it can be seen that nano ferrous sulfide particles are filamentous, but due to van der waals acting force, they have been agglomerated into larger chain-like agglomerates, and the modified nano ferrous sulfide composite material is more dispersed and uniform in distribution and only slightly agglomerated compared with nano ferrous sulfide.
Test example 2
The modified nano ferrous sulfide composite materials provided in examples 1 to 5 and the migration performance of the nano ferrous sulfide provided in comparative example 1 in a saturated porous medium were tested.
The detection method comprises the following steps: clean quartz sand was uniformly packed in a glass column having an inner diameter of 0.66cm and a length of 7 cm. After filling, firstly using CO for the sand column2Gas (purity)>99%) is aerated to remove residual air from the sand column. Then the sand column is washed by deionized water, and then the sand column is washed by a background electrolyte solution, so that the interior of the sand column is in an equilibrium state.
Before the sand column experiment is started, preparing injection of a material to be detected, mixing the material to be detected with a proper amount of background solution, and then fully stirring for 1h by using a magnetic stirrer; the well-stirred injection solution was transferred to a 100mL syringe and then pumped at 6.6 mL. multidot.h using a syringe pump-1Is injected into the sand column; the material to be detected being in the sand columnAfter equilibration, the sand column was flushed with the corresponding background electrolyte solution (without FeS) until the effluent could no longer detect Fe concentration. Collecting the effluent solution at the terminal of the sand column at intervals of 5min, completing sample measurement within 24h, and measuring the Fe mass concentration by adopting a phenanthroline colorimetric method.
The penetration curves of the modified nano ferrous sulfide composite materials provided in examples 1-5 and the nano ferrous sulfide provided in comparative example 1 in the saturated porous medium are shown in fig. 6.
The result shows that compared with the nanometer ferrous sulfide, the modified nanometer ferrous sulfide composite material has higher migration performance in a saturated porous medium, and the increase of the concentration of sericin is beneficial to enhancing the migration of the composite material.
Test example 3
The removal effects of the modified nano ferrous sulfide composite materials provided in examples 1 to 5, the nano ferrous sulfide provided in comparative example 1, and sericin on Cr (vi) in an aqueous solution were measured.
The detection method comprises the following steps: all experiments were performed in 50mL glass bottles, 10mL50 mg. multidot.L in 12.5mL deoxygenated water-1Adjusting the pH of the solution to 7 with hydrochloric acid and sodium hydroxide, and adding 2.5mL of 500 mg.L to the system-1The nano ferrous sulfide or sericin modified nano ferrous sulfide composite material or sericin is prepared by placing a glass bottle in a constant temperature oscillation box (25 ℃, 200 r.min)-1) Oscillating for 180min, and measuring the mass concentration of Cr (VI) by using inductively coupled plasma mass spectrometry.
The detection result is shown in fig. 7, and compared with the nano ferrous sulfide, the modified nano ferrous sulfide composite material provided in example 1 has a significantly improved Cr (vi) removing ability, which is improved from 65% to nearly 100%; the removal capacity of the modified nano ferrous sulfide composite material provided by the embodiment 2 on Cr (VI) is improved to 97%; the removal capacity of the modified nano ferrous sulfide composite material provided by the embodiment 3 on Cr (VI) is improved to 97%; the removal capacity of the modified nano ferrous sulfide composite material provided by the embodiment 4 on Cr (VI) is improved to 99%; the removal capacity of the modified nano ferrous sulfide composite material provided by the embodiment 5 on Cr (VI) is improved to 95%.
Compared with sericin and a comparative example, the sericin modified nano material has obviously improved Cr (VI) removing capability, and sericin and nano FeS can realize the synergistic removal of heavy metals in sewage.
Test example 4
The stability of the modified nano ferrous sulfide composite materials provided in examples 1-5 and the nano ferrous sulfide provided in comparative example 1 was determined.
The detection method comprises the following steps: freshly prepared 500 mg.L-1The nano ferrous sulfide and sericin modified nano ferrous sulfide composite material with different loading ratios is subjected to ultrasonic treatment for 30min, and then 40mL of material suspension is transferred into a 50mL glass bottle from a flask reactor. The anti-settling properties were analyzed by observing the settling distance and the color change of the solution and recorded photographically. Meanwhile, samples were taken from the upper solution at intervals (1, 3, 5, 10, 20, 30, 60, 720, 1440 min) and the total iron concentration in the solution was measured by phenanthroline colorimetry.
The detection result is shown in fig. 8, the nano ferrous sulfide substantially completely settles within 3min, the modified nano ferrous sulfide composite materials provided in examples 2 and 3 completely settle within 60min, and when the molar ratio of the sericin to the nano ferrous sulfide is greater than 0.001, the composite material still maintains a good stable state within 24h, which indicates that the anti-settling performance of the composite material is improved along with the increase of the sericin loading ratio.
Test example 5
The oxidation resistance of the modified nano ferrous sulfide composite materials provided in examples 1-5 and the nano ferrous sulfide provided in comparative example 1 was determined.
The detection method comprises the following steps: freshly prepared 500 mg.L-1The nano ferrous sulfide and sericin modified nano ferrous sulfide composite material with different loading ratios is subjected to ultrasonic treatment for 30min, and then 40mL of material suspension is transferred into a 50mL glass bottle from a flask reactor. Stirring was carried out for 60min under atmospheric conditions, and the soluble Fe (II) and the oxidation-reduction potential (ORP) were measured at intervals (1, 5, 10, 20, 30, 40, 50, 60 min).
The results of the tests are shown in figures 9-10,the dissolved concentration of Fe (II) measured in the suspension of the nano ferrous sulfide and modified nano ferrous sulfide composite material is gradually increased within the first 20min and then is exposed to atmosphere O2In the above case, Fe (II) is oxidized to Fe (III) and the concentration is lowered. Although a similar trend was observed in all tests, the Fe (II) concentration in the modified nano ferrous sulfide composite was lower than that of the nano ferrous sulfide, while the ORP of the sericin modified ferrous sulfide composite was also observed to be lower than that of the nano ferrous sulfide, indicating that sericin modification indeed significantly enhances the oxidation resistance of the nano ferrous sulfide.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A modified nano ferrous sulfide composite material is characterized in that the composite material comprises sericin and nano ferrous sulfide;
the carboxyl functional group of the sericin is combined on the surface of ferrous sulfide particles in a bidentate bridging mode;
in the composite material, the molar ratio of sericin to nano ferrous sulfide is (0.0001-0.005) in terms of ferrous ions: 1;
dispersing sericin in water under an anaerobic condition to form a suspension, then adding a ferrous salt aqueous solution into the suspension, uniformly mixing, dropwise adding a sulfide salt aqueous solution, reacting, standing, and drying to obtain the composite material.
2. The preparation method of the modified nano ferrous sulfide composite material as claimed in claim 1, wherein the sericin is dispersed in water at 30-60 ℃ to form a suspension; and/or the presence of a gas in the gas,
the molar ratio of the ferrous salt to the sulfide salt is (1.2-1): 1.
3. the method of claim 2, wherein the ferrous salt comprises (NH)4)2Fe(SO4)2·6H2O、FeSO4·7H2O and FeCl2·5H2At least one of O; and/or the presence of a gas in the gas,
the sulfide salt comprises Na2S·9H2O、Na2S2O4And CH3CSNH2At least one of (1).
4. The production method according to claim 2 or 3, characterized by further comprising a step of performing solid-liquid separation after standing.
5. The method according to claim 4, wherein the drying step is a step of drying a solid phase obtained by solid-liquid separation, and the drying includes at least one of vacuum drying, freeze drying and vacuum freeze drying.
6. Use of the modified nano ferrous sulfide composite material of claim 1 in treatment of wastewater containing heavy metals.
7. Use of the modified nano ferrous sulfide composite material of claim 1 in situ remediation of heavy metal contaminated groundwater.
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