CN114162952B - Nickel-sulfur composite micron zero-valent iron material and preparation method thereof - Google Patents
Nickel-sulfur composite micron zero-valent iron material and preparation method thereof Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a repairing agent for removing atrazine from nickel-sulfur composite micron zero-valent iron in an in-situ groundwater repairing technology and a preparation method thereof. The invention adds mZVI treated by dilute hydrochloric acid solution into water solution containing bivalent nickel and sulfuration reagent, and various chemical reactions occur on the surface of mZVI particles, so that sulfide is deposited on the surface of mZVI particles and nickel iron is rapidly replaced on the surface of mZVI particles, thereby achieving the purpose of simultaneously and rapidly synthesizing the second metal nickel-loaded and sulfuration modified micrometer zero-valent iron material by a one-step method. The one-step method for synthesizing the nickel-sulfur composite micron zero-valent iron material not only can improve the higher reactivity of ATZ, but also can improve the electron selectivity and the effective utilization rate of micron zero-valent iron, and has higher economic, environmental and social benefits.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a repairing agent for removing atrazine from nickel-sulfur composite micron zero-valent iron in an in-situ groundwater repairing technology and a preparation method thereof.
Background
Atrazine (ATZ), also known as atrazine, has been developed as a herbicide with a wide range of applications, with a maximum worldwide yield due to its good herbicidal properties. After being sprayed with wine, most ATZ directly enters the soil and enters deep soil or underground water through leaching. In addition, ATZ is an endocrine disrupter, and long-term exposure can have adverse effects on animal reproduction and human health. Meanwhile, ATZ has the characteristics of durability, enrichment, biotoxicity and the like. The ATZ has stable molecular structure, can exist in neutral, weak acid and weak base mediums stably, is not easy to degrade after being applied into the environment, has long residual period and higher permeability, and can migrate to groundwater environment through penetrating soil, thereby polluting soil, surface water and groundwater. Once the ATZ enters the groundwater environment, a persistent source of pollution is formed. Thus, widespread application of ATZ will cause serious pollution to soil and water in the environment. In addition, since ATZ acts as an endocrine disrupter, long-term exposure can have adverse effects on animals' reproduction and human health. Meanwhile, ATZ has the characteristics of cancerogenesis, teratogenesis and mutagenic three-cause, and has biological enrichment effect, namely, the ATZ can be enriched through each nutrition level of a food chain or a food network, so that the ATZ is harmful to human health. ATZ and its degradation products are frequently detected in groundwater, rivers and lakes due to the mass production and wide application, which indicates that pollution of ATZ has become a global ecological problem. The control and removal of ATZ contamination in groundwater has become one of the focus of attention and research in the related art. Therefore, the research and development of the repair medicament for removing the ATZ in the groundwater environment has important environmental significance.
Micro-scale zero-valent iron (mZVI) is widely used in groundwater remediation due to its high reactivity and strong reducibility. The in-situ reaction zone of the groundwater constructed by mZVI is a repair technology with great application prospect. In practical engineering applications, the repair efficiency and the on-site repair time of the mZVI technology on the target pollutant depend on the capability of continuously providing electrons as an electron donor on the mZVI surface in the pollutant degradation process. On the other hand, while mZVI has higher reactivity, it also reacts with a large amount of non-target contaminants present in groundwater while degrading the target contaminants, for example: h 2 O、Cl - 、NO 3 - 、SO 4 2- 、HPO 4 2- And HCO 3 - Etc., resulting in poor electron targeting. Therefore, in practical engineering of in-situ groundwater remediation, development of a remediation agent for achieving the final enhancement of the targeted removal capability of mZVI particles for removing target pollutants by improving the electron targeted transfer capability of mZVI for target pollutants is needed.
In recent years, surface modification of mZVI to increase reactivity of mZVI and enhance targeting of electrons has become a hot spot for improvement of the technology. Researches show that the vulcanizing layer formed on the surface of the mZVI particles through the reaction of the vulcanizing agent and the mZVI has loose structural characteristics and hydrophobic characteristics, and electrons generated by the zero-valent iron can flow to target pollutants more through inhibiting the competitive reaction of the mZVI and water, so that the purpose of regulating and controlling the surface components of the zero-valent iron is achieved. Therefore, the cost of the added zero-valent iron repair agent can be greatly saved in the engineering practical application. In addition, research shows that the second metal is loaded on the zero-valent iron, and the reactivity of the zero-valent iron can be effectively enhanced by forming a microcurrent effect or a catalytic effect. From this, it is deduced that the modification method of synchronously combining the vulcanization modification technology of the micrometer zero-valent iron and the second metal phase can not only remarkably improve the reactivity of the vulcanized micrometer zero-valent iron, but also greatly improve the selectivity to the target pollutants.
The invention comprises the following steps:
the invention provides a preparation method and application of a repair agent for removing atrazine in groundwater by preparing nickel-sulfur composite micron zero-valent iron by a one-step method in an in-situ groundwater repair technology. The method can effectively improve the efficiency of removing atrazine from groundwater by zero-valent iron and effectively inhibit the reaction between the material and non-target products (such as water). The method of the invention can greatly improve the reactivity of zero-valent iron on one hand, and obviously improve the electron selectivity and the utilization rate of mZVI on the other hand. The preparation method has the advantages of simple preparation process, environmental friendliness, short time consumption, easiness in realization of large-scale production and application, low cost and the like.
Summary of the invention:
in order to solve the problems of low effective utilization rate, poor electron targeting and the like of mZVI particles injected into a target aquifer in the in-situ reaction zone treatment technology of mZVI underground water. The invention provides a novel method for improving the efficiency and the electronic utilization rate of removing target pollutants by reducing zero-valent iron in the technology of in-situ groundwater remediation. The invention adds mZVI treated by dilute hydrochloric acid solution into water solution containing bivalent nickel and sulfuration reagent, and various chemical reactions occur on the surface of mZVI particles, so that sulfide is deposited on the surface of mZVI particles and nickel iron is rapidly replaced on the surface of mZVI particles, thereby achieving the purpose of simultaneously and rapidly synthesizing the second metal nickel-loaded and sulfuration modified micrometer zero-valent iron material by a one-step method. In order to verify the removal effect of the material on organic matters, the material is put into simulated groundwater containing ATZ, and the degradation effect of nickel-sulfur composite micron zero-valent iron on ATZ is examined.
The invention aims at realizing the following technical scheme:
in a buffer solution in an acidic environment, the micron zero-valent iron, the second metal nickel and the soluble sulfide salt are reacted simultaneously by a one-step method, and the prepared nickel-sulfur composite micron zero-valent iron has the sulfur-iron molar ratio S/Fe of 0.00125-1.0 and the nickel load ratio Ni/Fe of 0.5-10wt%.
The specific steps for preparing the nickel-sulfur composite micron zero-valent iron by the one-step method are as follows:
(A) Under normal temperature, untreated mZVI powder is added into a reactor in an anaerobic glove box, and then 1mol/L (hereinafter abbreviated as M) of HCl solution is added, uniformly mixed and kept still for 1h, so as to realize the pickling of mZVI by hydrochloric acid solution. After the pickling is finished, the mZVI is washed by high-purity water with the oxygen content less than 0.5g/mL, and the mZVI particles after the pickling by hydrochloric acid are obtained.
(B) Adding a deoxidized HAc-NaAc buffer solution into the reactor in the step (A), sealing by a cover, placing into a constant-temperature oscillating box, mixing at 25 ℃ and 300rpm for 10min, and adding a certain amount of Ni-containing alloy according to the mZVI addition in the step (A) 2+ The solution and the soluble sulfide salt solution are used for leading the reaction to reach the required nickel load ratio and the sulfur-iron molar ratio, and the reaction is continued under the conditions of 25 ℃ and 300 rpm. The Ni content in the solution was monitored by Atomic Absorption Spectrometry (AAS) until the Ni content in the solution was reduced to 0, which indicates that the Ni in the solution had been completely loaded onto the surface of mZVI particles.
(C) And (3) washing the solid material obtained in the step (B) with deoxidized absolute ethyl alcohol, washing with deoxidized high-purity water, and finally freeze-drying for 24 hours. And (3) filling nitrogen into the dried nickel-sulfur composite micron zero-valent iron, sealing the nickel-sulfur composite micron zero-valent iron in a bottle (the nitrogen content is 90-100%), and preserving the nickel-sulfur composite micron zero-valent iron at 4 ℃.
In the step (B) of preparing the nickel-sulfur composite micron zero-valent iron, the molar ratio S/Fe of sulfur and iron ranges from 0.00125 to 1.0, and the preferable molar ratio S/Fe of sulfur and iron ranges from 0.0125 to 0.1;
the nickel load ratio Ni/Fe ranges from 0.5 to 10wt percent, and the preferred Ni/Fe range is from 1 to 6wt percent;
the preferable pH value of the deoxidized HAc-NaAc buffer solution is 6;
the Ni-containing alloy 2+ Solution of NiCl 2 ·6H 2 O、NiSO 4 、Ni(CH 3 COO) 2 An aqueous solution of one of the nickel-containing metal salts;
the soluble sulfide salt solution is Na 2 S·9H 2 O、Na 2 S 2 O 4 、Na 2 S 2 O 3 And an aqueous solution of one of the sulfur-containing metal salts.
The modified front zero-valent iron (Ni/S-mZVI) is in the form of micron-sized powder particles, the scanning electron microscope chart shows regular spherical distribution (see figure 1 a) on the whole, wherein the micron zero-valent iron powder has the particle size of D 50 =5 to 30 μm. The nickel-sulfur composite micron zero-valent iron material prepared by the technical scheme of the invention still has good Fe 0 Crystalline forms and Fe is formed during the preparation process 3 O 4 (see FIG. 2). The Ni/S-mZVI greatly improves the removal effect of ATZ (see figure 3), and simultaneously greatly inhibits the side reaction of zero-valent iron and water, so that the hydrogen generated in the system is greatly reduced (see figure 4). Therefore, the nickel-sulfur composite micron zero-valent iron material synthesized by the one-step method can not only improve the higher reactivity of ATZ, but also improve the electron selectivity and the effective utilization rate of micron zero-valent iron.
Compared with the prior art, the invention has the following beneficial effects:
(1) The one-step method for synthesizing the nickel-sulfur composite micron zero-valent iron material (hereinafter referred to as Ni/S-mZVI) has wide sources of micron iron as a raw material and simple and easily obtained materials. The material has the advantages of simple synthesis method, quick reaction, mild reaction condition, short preparation time, easy operation, simple equipment, low synthesis cost and strong practicability, is favorable for large-scale popularization and application of the groundwater remediation technology, and has obvious economic, environmental and social effects.
(2) Compared with nano zero-valent iron with high reactivity, the Ni/S-mZVI prepared by the method has the characteristics of no spontaneous combustion, high safety, safer storage, more convenient transportation and the like.
(3) The Ni/S-mZVI prepared in the invention successfully introduces the second metal Ni into the vulcanized layer, thereby preparing the Ni/S-mZVI composite material. As the material has the catalysis performance of bimetal, the degradation capability of ATZ can be promoted, and the reactivity of zero-valent iron can be obviously improved.
(4) Compared with the traditional zero-valent iron technology, the prepared Ni/S-mZVI can effectively inhibit the reaction of the Ni/S-mZVI with non-target pollutants (water), so that the electron transfer efficiency of zero-valent iron is greatly improved, the removal rate of target pollutants by the added reactive material is greatly improved, the negative influence of the reactive material on the non-target pollutants is effectively reduced, the total capacity of the zero-valent iron for removing the pollutants is increased, the consumption of repair materials is greatly reduced, and the raw material cost is reduced.
(5) The technology has strong universality, is suitable for the repair process of groundwater pollution, is also suitable for the repair of surface water, industrial wastewater and the like, and can effectively reduce the sludge yield.
Drawings
FIG. 1 is a scanning electron microscope image of as-modified mZVI (a) and Ni/S-mZVI (b).
FIG. 2 is an X-ray diffraction pattern of as-modified mZVI and Ni/S-mZVI.
FIG. 3 is a graph of the efficiency of atrazine removal by zero valent iron material before and after modification in the present invention;
the abscissa represents the removal time (d), and the ordinate represents the ATZ removal rate (%).
FIG. 4 is a graph of hydrogen accumulation for as-modified mZVI and Ni/S-mZVI;
the abscissa indicates the removal time (d), and the ordinate indicates the hydrogen accumulation amount (mL).
Detailed Description
The technical solutions of the present invention will be further described with reference to the drawings in the embodiments of the present invention, but the present invention is not limited to these embodiments.
Example 1:
in an anaerobic glove box, 0.4g of iron powder and a proper amount of 10mM HCl solution are respectively added into a 130mL reactor at normal temperature, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; then 0.324mL of 100g/L NiCl is added 2 ·6H 2 O (Ni/fe=2wt%) solution, mixing at 25 ℃,300 rpm; after 10min, 0.4mLNa was injected 2 The S solution (solution concentration 1M, S/Fe=0.056) was reacted further at 25℃and 300 rpm. And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, and washing with deoxidized high-purity water for three times, freeze-drying and sealing for storage.
Example 2:
in an anaerobic glove box, 0.4g of iron powder and a proper amount of 10mM HCl solution are respectively added into a 130mL reactor at normal temperature, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; then 0.081mL of 100g/L NiCl is added 2 6H2O (Ni/Fe=0.5 wt%) solution, mixed at 25 ℃,300 rpm; after 10min 9. Mu.L Na was injected 2 The S solution (solution concentration 1M, S/Fe=0.00125) was reacted at 25℃and 300 rpm. And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. After the reaction is finished, using BAlcohol washing for three times, deoxidizing and washing with high-purity water for three times, freeze drying, and sealing and preserving.
Example 3:
in an anaerobic glove box under normal temperature, 0.4g of iron powder and a proper amount of 10mM of HCl solution are respectively added into a 130mL reactor, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; 1.62mL of 100g/L NiCl was further added 2 6H2O (Ni/Fe=10wt%) solution, mixed at 25deg.C, 300 rpm; after 10min 7.143mLNa was injected 2 The S solution (solution concentration 1M, S/Fe=1.0) was reacted at 25℃and 300 rpm. And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, and washing with deoxidized high-purity water for three times, freeze-drying and sealing for storage.
Example 4:
in an anaerobic glove box under normal temperature, 0.4g of iron powder and a proper amount of 10mM of HCl solution are respectively added into a 130mL reactor, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; 0.324mL of 100g/L NiSO was added 4 The solution was dissolved therein and mixed at 25℃and 300 rpm; after 10min, 0.2mLNa was injected 2 The S solution (concentration 1M) was reacted at 25℃and 300 rpm. And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, and washing with deoxidized high-purity water for three times, freeze-drying and sealing for storage.
Example 5:
under normal temperature, in an anaerobic glove box, 0.4g of iron powder and a proper amount of 10mM of HCl solution are respectively added into a 130mL reactor, evenly mixed, and kept still for 1h, and deoxidized high purity is used after the completionThe water was washed three times. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; 0.324mL of 100g/L Ni (CH) 3 COO) 2 The solution was dissolved therein and mixed at 25℃and 300 rpm; after 10min, 0.2mLNa was injected 2 The S solution (concentration 1M) was reacted at 25℃and 300 rpm. And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, deoxidizing, washing with high purity for three times, freeze-drying, and sealing and preserving.
Example 6:
in an anaerobic glove box under normal temperature, 0.4g of iron powder and a proper amount of 10mM of HCl solution are respectively added into a 130mL reactor, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; 0.324mL of 100g/L NiCl was added 2 ·6H 2 Dissolving O solution in the solution, and mixing at 25deg.C and 300 rpm; after 10min, 0.2mLNa was injected 2 S 2 O 4 The reaction was continued at 25℃and 300rpm (concentration 1M). And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, and washing with deoxidized high-purity water for three times, freeze-drying and sealing for storage.
Example 7:
in an anaerobic glove box under normal temperature, 0.4g of iron powder and a proper amount of 10mM of HCl solution are respectively added into a 130mL reactor, uniformly mixed, and kept still for 1h, and after the completion, the mixture is washed three times with deoxidized high-purity water. Adding 100ml of deoxidized HAc-NaAc buffer solution with pH value of 6 into a reactor, sealing by a cover, placing into a constant-temperature oscillating box, and mixing for 10min at 25 ℃ and 300 rpm; 0.324mL of 100g/L NiCl was added 2 ·6H 2 Dissolving O solution in the solution, and mixing at 25deg.C and 300 rpm; pouring after 10min0.2mLNa 2 S 2 O 3 The reaction was continued at 25℃and 300rpm (concentration 1M). And monitoring the Ni concentration in the reaction solution by using an atomic absorption spectrometer until the Ni concentration in the solution is 0, wherein the Ni in the solution is completely loaded on the mZVI particles. And (3) washing with ethanol for three times after the reaction is finished, and washing with deoxidized high-purity water for three times, freeze-drying and sealing for storage.
Example 8
This example provides a water treatment process for removing atrazine under anaerobic conditions using the nickel-sulfur composite micron zero-valent iron material prepared in example 1.
0.0292g NaCl, 0.0616g MgSO 4 ·7H 2 O、0.0555g CaCl 2 、0.0210g NaHCO 3 Dissolved in 500mL of high purity water. 0.02g of ATZ solid was weighed and dissolved in 10mL of methanol to give an ATZ mother liquor having a concentration of 2g/L, which was stored in a dark place. Into a 130mL reaction flask was added 100mL of the formulated deoxygenated simulated groundwater (DO<0.5 mg/L), 0.20mL of the mother liquor was removed therefrom, and 0.20mL of 2g/L ATZ mother liquor was added thereto, sealed with a rubber plug, and mixed well. 2.4g of the pre-modification mZVI and 2.4g of the nickel-sulfur composite micron zero-valent iron material prepared in the example 1 are respectively weighed and added into the reaction bottle, so that the concentrations of ATZ and the added pre-modification mZVI and the added nickel-sulfur composite micron zero-valent iron material in each reaction system are respectively 4mg/L, 24g/L and 24g/L. The reaction was carried out at 120rpm at 12℃and sampled and examined at the set time points. Each group was provided with 3 parallel systems.
As shown in FIG. 3, the removal rate of atrazine was the highest in preparation example 1Ni/SZVI and reached 66.2% when the reaction period reached 27 d.
From this, it is proved that the nickel-sulfur composite micron zero-valent iron Ni/S-mZVI can effectively promote ATZ degradation efficiency in groundwater environment.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.
Claims (10)
1. The nickel-sulfur composite micron zero-valent iron is characterized in that the micron zero-valent iron, second metal nickel and soluble sulfide salt are reacted simultaneously by a one-step method, and the preparation method comprises the following specific steps:
(A) Adding untreated micrometer zero-valent iron mZVI powder into a reactor, and then adding HCl solution to mix uniformly so as to realize pickling of mZVI by hydrochloric acid solution; after the pickling is finished, washing mZVI with high-purity water with oxygen content less than 0.5g/mL to obtain mZVI particles after the pickling with hydrochloric acid;
(B) Adding a deoxidized HAc-NaAc buffer solution into the reactor in the step (A), sealing, placing into a constant temperature oscillating box, mixing at 25deg.C and 300rpm for a period of time, and adding a certain amount of Ni-containing Ni according to the amount of mZVI in the step (A) 2+ The solution and the soluble sulfide salt solution lead the reaction to reach the required nickel load ratio and the sulfur-iron molar ratio, and the continuous reaction is continued under the conditions of 25 ℃ and 300 rpm; monitoring the Ni content in the solution by utilizing an atomic absorption spectrometry until the Ni content in the solution is reduced to 0;
(C) Washing the solid material obtained in the step (B) with deoxidized absolute ethyl alcohol, washing with deoxidized high-purity water, freeze-drying, and sealing for preservation;
the S/Fe molar ratio is 0.00125-1.0, and the Ni load ratio is 0.5-10wt%.
The method for preparing the nickel-sulfur composite micron zero-valent iron by a one-step method is characterized by comprising the following specific steps of:
(A) Adding untreated micrometer zero-valent iron mZVI powder into a reactor, and then adding HCl solution to mix uniformly so as to realize pickling of mZVI by hydrochloric acid solution; after the pickling is finished, washing mZVI with high-purity water with oxygen content less than 0.5g/mL to obtain mZVI particles after the pickling with hydrochloric acid;
(B) Adding the deoxidized HAc-NaAc buffer solution into the reactor in the step (A), sealing, placing into a constant temperature oscillating box, mixing at 25deg.C and 300rpm for a period of time, and adding according to mZVI in the step (A)In an amount, while adding a certain amount of Ni-containing 2+ The solution and the soluble sulfide salt solution lead the reaction to reach the required nickel load ratio and the sulfur-iron molar ratio, and the continuous reaction is continued under the conditions of 25 ℃ and 300 rpm; monitoring the Ni content in the solution by utilizing an atomic absorption spectrometry until the Ni content in the solution is reduced to 0;
(C) And (3) washing the solid material obtained in the step (B) with deoxidized absolute ethyl alcohol, washing with deoxidized high-purity water, and finally freeze-drying and sealing for storage.
3. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: step (a) is performed in an anaerobic glove box under normal temperature conditions.
4. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: the concentration of the hydrochloric acid solution in the step (A) was 1 mol/L.
5. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: the deoxygenated HAc-NaAc buffer solution in step (B) has a pH of 6.
6. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: the S/Fe molar ratio in the step (B) ranges from 0.00125 to 1.0, and the Ni load ratio ranges from 0.5 to 10wt%.
7. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 6, which is characterized in that: the S/Fe molar ratio in the step (B) ranges from 0.0125 to 0.1, and the Ni load ratio ranges from 1 to 6 wt%.
8. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: the composition described in step (B)Ni 2+ Solution of NiCl 2 ·6H 2 O、NiSO 4 、Ni(CH 3 COO) 2 An aqueous solution of one of them.
9. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: the soluble sulfide salt solution in the step (B) is Na 2 S·9H 2 O、Na 2 S 2 O 4 、Na 2 S 2 O 3 An aqueous solution of one of them.
10. The method for preparing nickel-sulfur composite micron zero-valent iron by the one-step method according to claim 2, which is characterized in that: and (3) filling nitrogen into the nickel-sulfur composite micron zero-valent iron obtained in the step (C), sealing in a bottle, and preserving at 4 ℃.
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