CN112808255B - Preparation method of modified nano ferrous sulfide composite material for removing water molybdate - Google Patents
Preparation method of modified nano ferrous sulfide composite material for removing water molybdate Download PDFInfo
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Abstract
The invention discloses a preparation method of a modified nano ferrous sulfide composite material for removing water molybdate, belonging to the technical field of environment functional composite nano materials. The preparation method comprises the following steps: firstly, preparing zirconium oxide with controllable granularity and higher purity by adopting a sol method, and then preparing zirconium oxide in N2And (2) after protection and uniform mixing by adding a ferrous chloride aqueous solution at a certain temperature, dropwise adding a sodium sulfide aqueous solution for reaction, standing and layering the obtained black suspension, and then rinsing the black suspension by adopting absolute ethyl alcohol obtained after nitrogen blowing, thereby obtaining the zirconium oxide modified nano ferrous sulfide composite material. The invention adopts a one-step coprecipitation method to synthesize the material, has simple preparation process and low cost of raw materials, and overcomes the defects of easy agglomeration and low reaction activity of ferrous sulfide. Compared with ferrous sulfide, the composite material has larger specific surface area, faster adsorption reaction rate and higher adsorption capacity, and obviously enhances the removal effect of molybdate in a water body.
Description
Technical Field
The invention belongs to the technical field of environment functional composite nano materials, and particularly relates to a preparation method and application of a zirconium oxide modified nano ferrous sulfide composite material for removing water molybdate, which is mainly applied to molybdenum-containing wastewater treatment.
Background
China is a big country for molybdenum ore production, and the molybdenum reserves are the second in the world. Due to the exploitation and selection of molybdenum ores and associated molybdenum ores, the generated industrial wastewater causes serious water and soil molybdenum pollution, such as molybdenum pollution events of the calabash island reservoir, Weinan molybdenum ore pollution events and the like. Molybdenum is an essential trace element in animals and plants, but excessive intake of molybdenum can cause adverse reactions such as arteriosclerosis, diarrhea, protein metabolism disorder and the like. Molybdenum mainly exists in the form of molybdate ion in natural water, and molybdate ion mainly exists in the form of MoO in neutral and alkaline water4 2-The morphology exists. Due to MoO4 2-Is relatively stable in the environment and is easily ingested by organisms in most systems, and when the concentration of molybdenum in the aqueous solution exceeds 5ppm, the molybdenum concentration causes harm to the surrounding environment and human health. The molybdenum content in the water around part of the molybdenum ore reaches 10mg/L, which is far higher than the limit value of the specific project standard of the surface water source of the centralized drinking water in the sanitary standard of the drinking water and the quality standard of the surface water environment of China by 0.07 mg/L. Therefore, the method for treating the molybdenum-polluted water has important significance for controlling and repairing the pollution of the molybdenum-polluted water body, and is efficient, economical and environment-friendly.
At present, the main methods for treating the molybdenum-containing wastewater at home and abroad comprise an ion exchange method, a chemical precipitation method, an adsorption method and the like, and the adsorption method has the characteristics of high efficiency, economy, simple and convenient operation and the like and is widely applied to treating heavy metal wastewater. The iron sulfide is widely present in anaerobic environments such as surface water sediments, underground water and the like. The environment-friendly ferrous sulfide is a precursor of common pyrite in nature, can transmit two electron donors of Fe (II) and S (-II), has strong reducibility and adsorbability, and can effectively remove various organic pollutants (such as lindane, nitrobenzene and the like) and heavy metals (such as chromium, mercury, arsenic and the like), so that the method for removing water molybdate by using the nano FeS has certain theoretical feasibility. However, the nano-FeS synthesis process is easy to generate agglomeration phenomenon, so that the reaction activity and the adsorption performance are reduced, and the application of the nano-FeS in practical engineering is limited, and therefore, the nano-FeS is necessary to be modified properly.
Research shows that Pd, Ni and Cu coated iron-based particles not only promote the generation and conversion of electrons, but also can be used for reducing pollutants and improving the reactivity of the iron-based particles. Some metal oxides such as TiO2、Al2O3And ZrO2Have proven to be effective materials for the selective separation of anions in aqueous solutions. However, compared with conventional inorganic heavy metal adsorbing materials such as iron oxide, aluminum oxide and the like, zirconium oxide has stronger acid and alkali resistance, and zirconium has strong ion affinity and coordination to oxygen-containing groups. In addition, the zirconia has larger adsorption capacity, excellent thermal and chemical stability and good dynamic performance, and can provide larger specific surface area. Therefore, zirconium (Zr) is introduced during the preparation of ferrous sulfide, and is dispersed on the surface of ferrous sulfide particles, so that the surface activity of the nano FeS can be theoretically improved, and the selective adsorption of heavy metal anions is facilitated. Therefore, the development of zirconium oxide modified ferrous sulfide for removing water body molybdate not only enriches the application approaches of ferrous sulfide, but also provides technical reference for the removal of anaerobic water body molybdate.
In the prior art, a preparation method of a modified ferrous sulfide composite material has been partially successful, for example, chinese patent No. 201710039858.2, published 2017, 05 and 31, discloses a patent document entitled "a preparation method and application of an alumina-supported nano ferrous sulfide composite material", in which a purchased alumina carrier is pretreated and then added to a ferrous sulfide suspension to obtain a mercury-removing adsorbent through processes of heating, stirring, drying and the like. Because the adsorbent is not nano-scale, the mercury removal effect is limited, and molybdate anions are different from mercury ions, so that the removal process and mechanism are obviously different; in addition, chinese patent application No.: 201810354563.9, published 2018, 10.09, a patent document entitled "magnesium-based ferrous sulfide composite nanomaterial and preparation method and application thereof" is disclosed, wherein the patent document refers to a composite material obtained by loading a magnesium-based material on the surface of ferrous sulfide to remove hexavalent chromium in a water body. Hexavalent chromium is similar to molybdate and is also a heavy metal anion, however, the pH range of the material for efficiently removing hexavalent chromium is narrow, so that the removal of molybdate ions in an alkaline environment is limited; meanwhile, the chemical property difference of magnesium and zirconium causes different pollutant removal mechanisms of the material; chinese patent application No.: 202010200466.1, published as 2020, 06, 12, discloses a patent document entitled "a ferrous sulfide composite material loaded on bimetal iron-copper, its preparation method and use", which is to load ferrous sulfide on bimetal iron-copper surface to improve the selectivity of the material to hexavalent chromium, but the preparation process of the material is complicated and the practical application is difficult.
In the research technology of zirconia materials, there are also patents in relevant aspects. As in chinese patent application No.: 201310115361.6, published 2013, 04 and 03, which discloses a patent document entitled "a method for removing trace heavy metals in water by using zirconium-loaded nano hybrid material"; chinese patent No.: 201110423329.5, published 2011 12.15.a method for preparing mesoporous zirconia is disclosed; chinese patent application No.: 201610494688.2, published 2016, 11, 16, which discloses a patent document entitled "a method for preparing high specific surface area hierarchical porous alumina-zirconia nanocrystals"; the zirconia composite material in the patent has a complex preparation process and has an unclear effect of removing molybdate in a water body.
In the research of molybdate removal, there are some better methods, for example, chinese patent application No.: 201610815698.1, published in 2017, 01 and 04.A patent document entitled "a method for preparing a biochar composite adsorbing material for removing molybdate from surface water" is disclosed, wherein the adsorbing material has low cost, but the preparation process is complex and the molybdate removing efficiency is low; chinese patent application No.: 201711232205.2, published in 2018, 04 and 20, the publication is entitled "a method for preparing water body hexavalent molybdate adsorbent based on waste iron and aluminum slime of water supply plants", which is cheap and easy to obtain, has low cost, but has low removal rate of molybdate, and the removal of molybdate in water body by the above two materials is greatly influenced by the acidity and alkalinity of the environment.
Disclosure of Invention
Aiming at the problems of defects and insufficiency of removing water body molybdate, easy agglomeration of nano ferrous sulfide and the like in the prior art, the invention aims to provide a preparation method of a zirconium oxide modified nano ferrous sulfide composite material for removing water body molybdate, so as to improve the reaction activity of the composite material and provide a technical reference for the actual removal of water body molybdate.
In order to solve the above problems, the present invention adopts the following technical solutions.
The invention provides a preparation method of a modified nano ferrous sulfide composite material for removing water molybdate, which comprises the following steps: firstly, preparing zirconium oxide with controllable granularity and higher purity by adopting a sol method, and then preparing zirconium oxide in N2And (2) after protection and uniform mixing by adding a ferrous chloride aqueous solution at a certain temperature, dropwise adding a sodium sulfide aqueous solution for reaction, standing and layering the obtained black suspension, and then rinsing the black suspension by adopting absolute ethyl alcohol obtained after nitrogen blowing, thereby obtaining the zirconium oxide modified nano ferrous sulfide composite material. The method specifically comprises the following steps:
(1) preparing a mixed solution of ethanol and water, adding zirconium salt to dissolve the mixed solution, placing the mixed solution in a wide-mouth bottle, sealing the wide-mouth bottle in a water bath kettle, and keeping the temperature at 70 ℃ for 2 hours to obtain zirconia sol and cooling the zirconia sol to normal temperature for later use. The volume ratio of the ethanol to the water is 5: 3.
(2) adding the zirconia sol prepared in the step (1) into a ferrous salt aqueous solution at the temperature of 30 ℃ in a nitrogen atmosphere, uniformly stirring in a three-neck flask provided with an electric stirrer, dropwise adding a sodium sulfide aqueous solution at a fixed speed through a separating funnel, continuously stirring the mixed solution for 20-30 min after the dropwise adding is finished, sealing, and standing to fully grow the nanoparticles.
The molar ratio of the ferrous salt to the sodium sulfide is 1: 1-1.2: 1; the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 10-1: 1.
(3) Standing for layering, removing supernatant, adding anhydrous ethanol with nitrogen gas, cleaning, sealing, and slowly stirring and mixing; and (4) standing and layering again, and repeating the steps for cleaning at least three times to obtain the zirconium oxide modified nano ferrous sulfide composite material.
Further, in the step (1), the zirconium salt is ZrOCl2·8H2O。
Further, in the step (2), the ferrous salt is FeCl2·4H2O。
Further, in the step (2), the molar ratio of the ferrous salt to the sodium sulfide is 1: 1.
Further, in the step (2), the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 2.
The modified nano ferrous sulfide composite material obtained by the preparation method can be applied to removal of surface water and anaerobic water molybdate.
The modified adsorption material has large specific surface area, shorter diffusion distance in particles and more surface reaction sites, thereby having higher adsorption capacity and faster reaction rate to Mo (VI).
The specific principle is presumed as follows:
the ferrous sulfide material has better removal effect under the acidic condition mainly due to MoO4 2-Converted into Mo which is easier to have adsorption, flocculation and sedimentation effects8O26 4-，Mo7O24 6-And HMo7O24 5-And the like, compared with a ferrous sulfide material, the material modified by zirconia has smaller influence on the removal of water molybdate by the acidity and alkalinity of the environment, and the removal efficiency of the modified composite material is higher. Mainly caused by the strong ion exchange effect of Zr-OH on the surface of the material to molybdenum. Zirconia is a weakly alkaline oxide, and amorphous hydrated zirconia has the characteristics of high hydroxyl content and large specific surface area. After the zirconium oxide is used for modifying the ferrous sulfide, the molybdate can be directly adsorbed through hydroxyl on the surface of the zirconium oxide, and the electron transmission capability of the ferrous sulfide is activated, so that the removal rate and the removal amount of the molybdate in the water body by the composite material are improved.
The adsorption mechanism of molybdate on the zirconia surface can be expressed as:
2Zr-OH+MoO4 2-＝Zr2MoO4+2OH-
mo (VI) on the surface of the FeS further generates adsorption action to remove:
the removing mechanism of the zirconium oxide modified nano ferrous sulfide composite material to molybdate mainly comprises the actions of ion exchange and coordination adsorption.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process is simple, the modified composite material is synthesized by a one-step coprecipitation method, the raw material cost is low, the removal efficiency is high, and the application range is wide. In the preparation process, the problems of easy agglomeration, low reaction activity and the like of ferrous sulfide are solved by optimizing the conditions of the zirconium-iron ratio, the temperature, the stirring speed and the like, and the mass transfer rate and the dispersity of the nano particles are improved.
(2) The composite material can effectively remove water molybdate, and the removal rate (more than 80%) of the zirconia modified nano ferrous sulfide composite material to Mo (VI) is far higher than that of FeS (less than 60%) when the initial concentration of Mo (VI) is 10mg/L and the pH of the initial solution is 4.0-9.0. The maximum adsorption capacity of the Mo (VI) with the initial concentration of 10mg/L can reach 89.42mg/g, and the reaction process can reach equilibrium within 40 min.
(3) Compared with ferrous sulfide, the composite material has larger specific surface area, faster adsorption reaction rate and higher adsorption capacity, obviously enhances the removal effect of water molybdate, and has little influence on the removal of the water molybdate by the acidity and alkalinity of the environment.
Drawings
Fig. 1 is a scanning electron microscope image of the zirconia-modified nano ferrous sulfide composite material obtained in example 2 of the present invention.
FIG. 2 is a diagram of the spectrum analysis of the zirconia-modified nano ferrous sulfide composite material obtained in example 2 of the present invention.
FIG. 3 is a graph showing the adsorption effect of zirconium oxide modified nano ferrous sulfide composite materials with different proportions on Mo (VI) at different pH values, which are obtained in examples 1 to 3 of the present invention.
Fig. 4 is a graph comparing the removal performance of the zirconia-modified nano ferrous sulfide composite material and the unmodified nano ferrous sulfide material obtained according to the example 2 and the comparative example under different pH conditions.
FIG. 5 is a graph of the adsorption kinetics process of the zirconia-modified nano ferrous sulfide composite material obtained in example 2 of the present invention on sewage with an initial concentration of 10mg/L Mo (VI).
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the present invention is not limited thereto.
Example 1
The embodiment provides a preparation method of a zirconium oxide modified nano ferrous sulfide composite material (the modification ratio of zirconium is 0.1, namely the molar ratio of zirconium oxide to ferrous sulfide is 1:10), which comprises the following steps:
(1) preparing zirconia sol: preparing 13mL of ethanol and water, wherein the weight ratio of ethanol to water is 5: 3(v/v), then 0.645g ZrOCl was weighed2·8H2And adding the O into the mixed solution for dissolving, transferring into a wide-mouth bottle, sealing in a water bath kettle, heating to 70 ℃, and preserving heat for 2 hours. And sealing and cooling the obtained zirconia sol to normal temperature for later use.
(2) Preparing a zirconium oxide modified nano ferrous sulfide composite material: weighing high-purity FeCl23.977g of the product is dissolved in 100mL of high-purity water aerated with nitrogen, transferred into a three-neck flask which is placed in a constant-temperature water bath kettle at the temperature of 30 ℃ in advance, continuously introduced with nitrogen (the flow rate is 500mL/min) and stirred (the rotation speed is 300rpm/min) for 15 min; adding 13mL0.154mol/L zirconia sol prepared in the step (1), and fully stirring for 15min to obtain a uniform and oxygen-free mixed solution; weighing 4.804gNa2S·9H2Dissolving O in 100mL of deoxygenated water, adding dropwise (1 drop/second) into the mixed solution through a separating funnel to enable the Fe: S (molar ratio) in the solution to be 1:1, stirring at constant temperature until the reaction is completed, continuously introducing nitrogen (flow rate of 500mL/min) and stirring (rotating)Speed 300rpm/min) for 30min, and obtaining black suspension in N2Quickly transfer to brown jar seal under protection.
(3) And (3) rinsing: standing for 24 hr, slightly sucking off supernatant with a pipette under nitrogen protection, adding anhydrous ethanol with equal amount of nitrogen gas, sealing, stirring at low speed (150rpm/min) for 10min, standing for 5 hr for layering, repeating the above steps, and cleaning for three times to remove Na+、Cl-Making plasma to obtain a zirconium oxide modified nano ferrous sulfide composite material (theoretical ZrO)2/FeS＝0.1)。
Example 2
The embodiment provides a preparation method of a zirconium oxide modified nano ferrous sulfide composite material (the modification ratio of zirconium is 0.5, namely the molar ratio of zirconium oxide to ferrous sulfide is 1:2), which comprises the following steps:
(1) the pretreatment of the zirconia sol was as described in example 1, step (1). Except that 3.223g of ZrOCl were weighed2·8H2O dissolved in 65mL ethanol and water 5: 3 (v/v).
(2) The preparation of the zirconia-modified nano ferrous sulfide composite was as described in step (2) of example 1. Except that 65ml of 0.154mol/L of zirconia sol was added.
(3) The rinsing procedure was the same as that described for (theoretical ZrO) in step (3) of example 12/FeS＝0.5)。
As can be seen from the scanning electron microscope image in fig. 1, the zirconia-modified nano ferrous sulfide composite material obtained in the present embodiment has uniform dispersion and a large specific surface area.
As can be seen from the energy spectrum analysis chart of fig. 2, the main elements of the composite material obtained in this example are S, Fe and Zr, wherein the atomic fraction of Zr is 20.28%, which indicates that the modified adsorbent material has been loaded with zirconium element.
Example 3
The embodiment provides a preparation method of a zirconium oxide modified nano ferrous sulfide composite material (the modification ratio of zirconium is 1.0, namely the molar ratio of zirconium oxide to ferrous sulfide is 1:1), which comprises the following steps:
(1) the pretreatment of the zirconia sol was as described in example 1, step (1). Except that 6.445g of ZrOCl were weighed2·8H2O dissolved in 130mL ethanol and water 5: 3 (v/v).
(2) The preparation of the zirconia-modified nano ferrous sulfide composite was as described in step (2) of example 1. Except that 130ml of 0.154mol/L of zirconia sol was added.
(3) The rinsing procedure was the same as that described for (theoretical ZrO) in step (3) of example 12/FeS＝1.0)。
Example 4
The embodiment provides a preparation method of a zirconium oxide modified nano ferrous sulfide composite material (the modification ratio of zirconium is 0.5, namely the molar ratio of zirconium oxide to ferrous sulfide is 1:2) at 20 ℃, and the method comprises the following steps:
(1) the pretreatment of the zirconia sol was as described in example 2, step (1).
(2) The preparation of the zirconia-modified nano ferrous sulfide composite was as described in step (2) of example 2. Except that the temperature of the water bath during the reaction was 20 ℃.
(3) The rinsing procedure was as described in step (3) of example 2.
Comparative example:
the present comparative example provides a method of preparing a nano ferrous sulfide material, the method comprising the steps of:
(1) preparing a nano ferrous sulfide material: weighing high-purity FeCl23.977g of the product is dissolved in 100mL of high-purity water aerated with nitrogen, transferred into a three-neck flask which is placed in a constant-temperature water bath kettle at the temperature of 30 ℃ in advance, continuously introduced with nitrogen (the flow rate is 500mL/min) and stirred (the rotation speed is 300rpm/min) for 15 min; 4.804g of Na were weighed out2S·9H2Dissolving O in 100mL of deoxygenated water, adding dropwise (1 drop/second) into the mixed solution through a separating funnel to enable Fe: S (molar ratio) in the solution to be 1:1, stirring at constant temperature until the reaction is completed, continuously introducing nitrogen (flow rate of 500mL/min) and stirring (rotation speed of 300rpm/min) for 30min, and adding the obtained black suspension into N2Quickly transfer to brown jar seal under protection.
(2) Rinsing: standing for 24h, and keeping in nitrogenGently sucking off supernatant with pipette under protection, adding anhydrous ethanol with equal amount of nitrogen gas, sealing, stirring on magnetic stirrer at low speed (150rpm/min) for 10min, standing for 5 hr for layering, repeating the above steps, and cleaning for three times to remove Na+、Cl-And (4) redundant ions are carried out, so that the unmodified nano ferrous sulfide material is obtained.
Zirconia modified nano ferrous sulfide composite materials with different modification ratios (the modification molar ratios are 0.1, 0.5 and 1.0 respectively) prepared by the preparation methods shown in examples 1 to 3 are used as adsorbents to treat Mo (VI) containing wastewater simulated in laboratories. As shown in FIG. 3, after the reaction reaches equilibrium, the removal rate of molybdenum of 10mg/L can be maintained above 75.26% for all three kinds of composite materials with modified zirconium addition under the conditions of initial pH values of 5, 7 and 9, and the maximum removal rate is 91.53%. It can be seen that the removal rate of the material with the Zr-Fe ratio of 0.5 is obviously higher than that of the material with the Zr-Fe ratio of 0.1 to molybdenum, the removal rate of the material with the Zr-Fe ratio of 1.0 is slightly increased relative to that of the material with the Zr-Fe ratio of 0.5, and the optimal modification ratio of the selected zirconia modified nano ferrous sulfide composite material is 0.5 in comprehensive consideration.
The zirconia-modified nano ferrous sulfide composite material prepared in example 2 and the nano ferrous sulfide material prepared without adding zirconia sol in the comparative example are respectively used as adsorbents to treat molybdenum-containing wastewater simulated in a laboratory. The experimental result is shown in fig. 4, and it can be seen from fig. 4 that the removal of molybdenum from nano FeS is greatly influenced by pH, when the pH is increased from 4.0 to 5.0, the removal rate is rapidly decreased from 57.58% to 36.44%, and the removal rate of mo (vi) is also continuously decreased with the increase of pH. And ZrO2The removal rate of Mo (VI) by the/FeS is relatively less influenced by the change of pH, wherein ZrO2The removal rate of/FeS at pH 4 was 89.42%, which resulted in a significantly enhanced molybdenum removal capacity of the modified material.
Example 2 results of kinetics experiments for removing Mo (VI) from water by zirconia-modified nano ferrous sulfide composite material (modification ratio 0.5) are shown in FIG. 5. from FIG. 5, it can be seen that for an initial Mo (VI) concentration of 10mg/L, when ZrO is present2When the dosage of the/FeS material is increased from 20mg/L to 200mg/L, the molybdenum removal rate is also increased from 22.14 percent to 97.13% adsorption curve reached essentially equilibrium after 40min, showing excellent removal performance.
The nano ferrous sulfide materials prepared in the above examples 1 to 4 and comparative example were subjected to molybdenum removal adsorption test, respectively, with the addition of 100mg/L of the adsorption material and Na for the experiment2MoO4·2H2And O is self-prepared into the molybdenum-containing wastewater, and the concentration of molybdate is 10 mg/L. The adsorption time was 6 hours, the water temperature was 25 ℃ and the oscillation speed was 180 rpm.
The test data show that the adsorbing materials obtained in the examples 1 to 4 of the present invention have very significant removal efficiency of molybdate in wastewater (as shown in table 1). At initial pH 5, 7, 9, the removal rate of the adsorption materials 1-4 for molybdenum was significantly higher than the removal rate of the comparative adsorption material.
TABLE 1 results of the molybdenum removal experiments in the different examples
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Removal Rate (%) at initial pH of 5 | 84.79 | 86.40 | 87.60 | 73.32 | 36.44 |
| Removal Rate (%) at an initial pH of 7 | 81.73 | 88.74 | 91.53 | 75.21 | 28.59 |
| Removal Rate (%) at an initial pH of 9 | 75.25 | 78.97 | 81.38 | 60.38 | 18.42 |
Claims (6)
1. A preparation method of a modified nano ferrous sulfide composite material for removing water molybdate is characterized by comprising the following steps:
(1) preparing a mixed solution of ethanol and water, adding zirconium salt to dissolve the mixed solution, placing the mixed solution in a wide-mouth bottle, sealing the wide-mouth bottle in a water bath kettle, and keeping the temperature at 70 ℃ for 2 hours to obtain zirconia sol and cooling the zirconia sol to normal temperature for later use;
the volume ratio of the ethanol to the water is 5: 3;
(2) adding the zirconia sol prepared in the step (1) into a ferrous salt aqueous solution at the temperature of 30 ℃ in a nitrogen atmosphere, uniformly stirring in a three-neck flask provided with an electric stirrer, dropwise adding a sodium sulfide aqueous solution at a fixed speed through a separating funnel, continuously stirring the mixed solution for 20-30 min after the dropwise adding is finished, sealing, and standing to fully grow the nanoparticles;
the molar ratio of the ferrous salt to the sodium sulfide is 1: 1-1.2: 1; the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 10-1: 1;
(3) standing for layering, removing supernatant, adding anhydrous ethanol with nitrogen gas, cleaning, sealing, and slowly stirring and mixing; and (4) standing and layering again, and repeating the steps for cleaning at least three times to obtain the zirconium oxide modified nano ferrous sulfide composite material.
2. The preparation method of the modified nano ferrous sulfide composite material for removing water molybdate according to claim 1, which is characterized by comprising the following steps: in the step (1), the zirconium salt is ZrOCl2·8H2O。
3. The preparation method of the modified nano ferrous sulfide composite material for removing water molybdate according to claim 1, which is characterized by comprising the following steps: in the step (2), the ferrous salt is FeCl2·4H2O。
4. The preparation method of the modified nano ferrous sulfide composite material for removing water molybdate according to claim 1, which is characterized by comprising the following steps: in the step (2), the molar ratio of the ferrous salt to the sodium sulfide is 1: 1.
5. The preparation method of the modified nano ferrous sulfide composite material for removing water molybdate according to claim 1, which is characterized by comprising the following steps: in the step (2), the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 2.
6. The application of the modified nano ferrous sulfide composite material obtained by the preparation method according to any one of claims 1 to 5 in removing molybdate from surface water bodies and anaerobic water bodies.
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| CN106536097A (en) * | 2015-11-06 | 2017-03-22 | 浙江工业大学 | Preparation method for iron-ferrous sulfide composite |
| CN108620047A (en) * | 2018-04-19 | 2018-10-09 | 华南理工大学 | A kind of magnesium-based ferrous sulfide composite nano materials and its preparation method and application |
| CN108726577A (en) * | 2018-06-22 | 2018-11-02 | 济宁学院 | A kind of preparation method of ferrous sulfide nanometer sheet material |
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| CN108620047A (en) * | 2018-04-19 | 2018-10-09 | 华南理工大学 | A kind of magnesium-based ferrous sulfide composite nano materials and its preparation method and application |
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