CN112844330B - Preparation method and application of chitosan-stabilized zirconium-modified nano ferrous sulfide composite material - Google Patents
Preparation method and application of chitosan-stabilized zirconium-modified nano ferrous sulfide composite material Download PDFInfo
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Abstract
The invention provides a preparation method and application of a chitosan stabilized zirconium modified nano ferrous sulfide composite material, and belongs to the technical field of environment functional composite nano materials. The preparation method specifically comprises the following steps: firstly, preparing zirconium oxide with controllable granularity and higher purity by a sol method, and dissolving chitosan by using a dilute acid solution; and then adding a ferrous chloride solution into the chitosan solution under the protection of nitrogen, stirring uniformly, adding zirconia sol, continuously stirring, dropwise adding a sodium sulfide solution for reaction, and standing to obtain the chitosan-stabilized zirconium modified nano ferrous sulfide composite material. The material is synthesized by adopting a one-step coprecipitation method, so that the raw material cost is low, the preparation process is simple, the defects of easiness in agglomeration of ferrous sulfide, low reaction activity and poor stability are overcome, the more stable removal effect on water body molybdate is realized, and the material has good market application prospect for treating molybdenum pollution of surface water and underground water.
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 chitosan-stabilized zirconium-modified nano ferrous sulfide composite material for removing water molybdate, which is mainly applied to molybdenum-containing wastewater treatment.
Background
The heavy metal molybdenum is a trace element necessary for plants and animals and is also an important mineral resource. In recent years, with the application of a large amount of heavy metal molybdenum, the exploitation of the heavy metal molybdenum is increased year by year, and the tailings drainage containing high-concentration molybdenum brings certain harm to the surrounding environment. Such as molybdenum pollution events of the calabash island reservoir, Weinan molybdenum ore pollution events, Henan Loyan Koelreuterite pollution events and the like. The concentration of molybdenum detected in partial water systems at present varies from dozens of mug/L to mg/L, and the maximum pollution limit value of molybdenum in drinking water specified in China is 0.07 mg/L. Molybdenum in the aqueous solution has more valence state (+ 2- +6), wherein in a neutral alkaline environment, hexavalent molybdenum mainly adopts molybdate ions (MoO)4 2-) The existing form has the characteristics of strong toxicity, relative stability in the environment, easy biological uptake and the like. Thus MoO in wastewater4 2-The removal of (A) has very important environmental significance. At present, methods such as chemical precipitation, ion exchange and adsorption are already used for treating molybdenum-containing wastewater, and the adsorption method is widely applied due to the characteristics of high efficiency, economy and easy operation. The development of the adsorbent which is low in cost, environment-friendly and high in molybdenum removal performance has important practical significance.
The ferro-sulphur has been widely paid attention to the aspect of removing heavy metals in wastewater as a strong reducing agent, and ferrous sulfide is a precursor of common pyrite in nature and widely exists in anaerobic environments such as soil, river sediment, underground water and the like. Due to the unique surface chemical property and molecular structure, the amorphous ferrous sulfide can remove heavy metals such as chromium, mercury and arsenic and organic pollutants such as lindane and nitrobenzene by mechanisms such as adsorption, ion exchange, fixation and the like. Therefore, the method for removing water body molybdate by using the nano FeS has certain theoretical feasibility. The nano FeS has the excellent characteristics of large specific surface area, strong reactivity and the like, but is easy to generate agglomeration, oxidation and inactivation in the synthesis, use and storage processes, so that the application of the nano FeS in practical engineering is limited, and therefore, the nano FeS is necessary to be modified to improve the stability of the nano FeS.
Chitosan is a biopolymer extracted from crustacean shells or fungal biomass, and has wide sources, easy availability and low price. The high proportion of amino functional groups in the natural polymer can generate higher binding performance to metal ions such as cadmium, copper, lead, mercury and chromium. If the nano particles are wrapped on the surfaces of the nano particles, the double electric layers of the nano particles are increased, the agglomeration of the nano particles is effectively inhibited, the possibility of contact of the nano particles with oxygen is reduced, and the oxidative deterioration of the nano particles is slowed down. However, the adsorption performance of chitosan is controlled by the diffusion process, whether from the reaction equilibrium or the kinetic process. In order to ensure that the ferrous sulfide nanoparticles have reaction activity and a faster reaction rate, the zirconium oxide with good kinetic performance is introduced while the chitosan wraps the ferrous sulfide. According to the report, zirconia has both reducibility and surface hydroxyl, and has strong ion affinity and coordination on oxygen-containing groups, so that the surface activity and mass transfer rate of nano FeS modified by adding zirconia can be theoretically improved. In a word, the combined modification of the nano FeS by adopting the chitosan and the zirconium oxide is expected to develop a composite functional material with good removal performance and high stability, and has important significance for repairing the heavy metal molybdenum pollution of the water body.
In the prior art, the preparation method of related modified composite materials has partial achievements, such as Chinese patent application number: 201610815698.1, published as 2017, 01 month 04, which discloses a patent document entitled "a method for preparing a biochar composite adsorbing material for removing molybdate from surface water"; chinese patent application No.: 201711232205.2, published as "a method for preparing water body hexavalent molybdate adsorbent based on waste iron and aluminum slime of water supply plant", published as 2018, 04 and 20 days; although the two adsorbing materials have low cost, the removing rate of molybdate in the water body is low, and the adsorbing materials are greatly influenced by the acidity and the alkalinity of the environment. Chinese patent application No.: 201610022704.8, published 2016, 01, 14, discloses a patent entitled "preparation method and application of ferrous sulfide/biochar compositeIn the patent, biological carbon is used as a carrier to load sodium carboxymethylcellulose modified ferrous sulfide nanoparticles to prepare a Cr (VI) removing composite material with adsorption and redox capabilities, but the preparation steps of the biological carbon are complex and are not beneficial to industrial application. Chinese patent application No.: 201610297139.6, published 2016, 09 and 28, discloses a patent document entitled "a zirconium modified composite adsorbent and its preparation method and application", which is a defluorination adsorbent with good mechanical properties prepared by combining zirconium modified chitosan, zeolite and kaolin; chinese patent application No.: 201911370005.2, published 2019, 12 and 26, discloses a patent document entitled "a method for preparing a modified chitosan fluoride ion adsorbent", which is prepared by dissolving the modified chitosan fluoride ion adsorbent with acetic acid, performing pore formation with ethanol, curing with sodium hydroxide, and crosslinking with epichlorohydrin to form chitosan porous microspheres; then modifying by using a mixed solution of ferric nitrate, aluminum nitrate and zirconium nitrate, further crosslinking epichlorohydrin, and then washing, drying and the like to obtain the epoxy chloropropane modified epoxy resin; the two adsorbing materials are both coated and modified by chitosan, but the removal process and mechanism are different due to different core materials and different pollutant removal; chinese patent application No.: 201610485863.1, application laid-open No. 2016, 06, 29, disclosing a patent document entitled "a preparation method of a sulfhydrylation magnetic chitosan composite material for removing heavy metal ions", the invention uses sulfhydrylation functionalized chitosan quaternary ammonium salt derivative as a carrier material, and a reversed phase suspension crosslinking method is used for coating ferroferric oxide to prepare the composite material; but the preparation process contains paraffin, span 80 and ethyl acetate surfactant, so that the cost is high and the preparation process is complex. Other examples are, chinese patent application nos.: 201710879753.8, published 2017, 12 and 19, which discloses a patent document entitled "a method for preparing titanium dioxide and chitosan composite material"; chinese patent application No.: 201610835532.6, published 2017, 02, 08, and entitled "A method for adsorbing Pb in Water2+Patent documents of Zr/chitosan composite adsorbent and preparation method thereof "; chinese patent application No.: 202010268387.4, disclosureA patent document named 'amino-rich compound modified chitosan-zirconium composite gel ball and preparation and application thereof' is disclosed in 2020, 04 and 08 days; chinese patent application No.: 201210347682.4, published as "magnetic chitosan/nano-Fe", 09 month 18, 20123O4Patent documents of composite materials and methods for their preparation "; the research results are mostly used for treating volatile organic compounds or metal ions in a cationic state in water, are not suitable for removing molybdate existing in water as anions, and the preparation process of the materials is complex, and the used cross-linking agent is easy to cause secondary pollution to water quality and is not beneficial to industrial production.
Disclosure of Invention
Aiming at the problems of the prior art that water body molybdate is not removed, nano ferrous sulfide is easy to agglomerate and oxidize, and the stability is poor, the invention aims to provide a preparation method of a chitosan stabilized zirconium modified nano ferrous sulfide composite material for removing water body molybdate, so that the reaction activity and the stability of the composite material can be improved, and meanwhile, a technical reference is provided 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 relates to a preparation method of a chitosan stabilized zirconium modified nano ferrous sulfide composite material, which comprises the steps of firstly preparing zirconium oxide with controllable granularity and higher purity by a sol method, and dissolving chitosan by a dilute acid solution; then adding a ferrous chloride solution into the chitosan solution under the protection of nitrogen, stirring uniformly, adding zirconia sol, continuously stirring, dropwise adding a sodium sulfide solution for reaction, standing to obtain the chitosan stabilized zirconium modified nano ferrous sulfide composite material, and specifically comprising the following steps of:
(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 70 ℃ water bath kettle, and preserving heat for 2 hours to obtain clear and transparent zirconia sol and cooling the clear and transparent zirconia sol to normal temperature for later use. The volume ratio of the ethanol to the water is 5: 3.
(2) preparing 1-5% by mass of diluted acid solution by using high-purity water, slowly adding chitosan, fully stirring and dissolving, and continuously introducing nitrogen to ensure that the uniformly-mixed and oxygen-free chitosan solution is obtained.
(3) Slowly adding the chitosan solution prepared in the step (2) into a ferrous salt aqueous solution prepared from deoxygenated water at 30 ℃ in a nitrogen atmosphere, continuously stirring for 15min in a three-neck flask provided with an electric stirrer, adding the zirconia sol prepared in the step (1), continuously stirring and continuously introducing nitrogen, uniformly stirring, dropwise adding a sodium sulfide aqueous solution prepared from the deoxygenated water at a fixed speed through a separating funnel, continuously stirring the mixed solution for 20-30 min after dropwise adding is finished, sealing and standing for 24-36 h to fully grow nanoparticles, thereby obtaining the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material.
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; the mass ratio of the chitosan to the ferrous sulfide is 1: 10-1: 2.
Further, in step 1, the zirconium salt is ZrOCl2·8H2O。
Further, in step 2, the dilute acid is one of hydrochloric acid, nitric acid, acetic acid and benzoic acid.
Further, in the step 3, the molar ratio of the ferrous salt to the sodium sulfide is 1: 1; the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 2; the mass ratio of the chitosan to the ferrous sulfide is 3: 10.
Further, in step 3, the ferrous salt is FeCl2·4H2O。
The invention prepares a chitosan stabilized zirconium modified nano ferrous sulfide composite material by a one-step coprecipitation method.
The chitosan stabilized zirconium modified nano ferrous sulfide material prepared by the invention can be applied to removing heavy metal molybdenum in surface water bodies and underground water.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method is simple, the modified composite material is synthesized by a one-step coprecipitation method, and an optimization experiment shows that the modified material, namely the zirconium oxide and the ferrous sulfide, have a molar ratio of 1:2, and the optimal removal rate of molybdate in a water body is achieved when the mass ratio of the chitosan to the ferrous sulfide is 3:10 (the removal rate can reach 82.37% when the concentration of molybdenum is 10 mg/L).
(2) In the preparation process, the ferrous sulfide is modified jointly by adding organic and inorganic materials, so that the composite material has coupling and dispersing functions, plays a role in synergy, solves the problems of easy agglomeration, low reaction activity, poor stability and the like of the ferrous sulfide, expands the application range of the ferrous sulfide nano material and is convenient for practical application.
(3) The modified material of the invention is zirconia and chitosan, the raw material source is wide, the price is low, and the chitosan can be biodegraded, belonging to renewable resources and environment-friendly materials. The chitosan contains abundant adsorption functional groups (amino and hydroxyl), and improves the adsorption capacity of heavy metal molybdenum.
(4) The chitosan stabilized zirconium modified nano ferrous sulfide composite material has good market application prospect in treating molybdenum pollution of surface water and underground water.
Drawings
Fig. 1 is a scanning electron microscope image of the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material obtained in example 2 of the present invention.
FIG. 2 is a graph showing the adsorption effect of chitosan-stabilized zirconium-modified nano ferrous sulfide composite materials obtained in examples 1 to 3 of the present invention on Mo (VI).
Fig. 3 is a graph comparing the removal performance of the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material and the unmodified nano ferrous sulfide material obtained in example 2 of the present invention at different pH values.
Fig. 4 is a comparison graph of the stabilities of the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material and the unmodified nano ferrous sulfide material obtained in example 2 of the present invention.
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.
The modified adsorption material is rough and porous, contains rich amino and hydroxyl, has improved oxidation resistance and stability, and has more surface reaction sites for nano ferrous sulfide, thereby having higher adsorption capacity for Mo (VI).
The specific principle is presumed as follows:
amino groups on the surface of the chitosan are ionized in an aqueous solution, and formed cations can be electrostatically adsorbed with negatively charged molybdate ions. Zirconium oxide is a weakly alkaline oxide, and amorphous hydrated zirconium oxide has the characteristics of high hydroxyl content and large specific surface area, so that molybdenum can be removed by ion exchange through Zr-OH (shown as formula 1); and the doping of the zirconium Ions (IV) to the ferrous sulfide improves the lattice defect of active components in the ferrous sulfide, promotes the transfer of electrons, and the synergistic effect of the zirconium Ions (IV) and the ferrous sulfide enhances the reaction activity of the composite material (as shown in formula 2).
The possible reaction mechanisms are:
2Zr-OH+MoO4 2-＝Zr2MoO4+2OH-(formula 1)
The results of specific part of the experimental tests are as described in the specific examples.
Example 1
The embodiment provides a preparation method of a chitosan-stabilized zirconium-modified nano ferrous sulfide composite material (the molar ratio of zirconium oxide to ferrous sulfide is 1:2, and the mass ratio of chitosan to ferrous sulfide is 1: 10), which comprises the following steps:
(1) preparing zirconia sol: preparing 65mL of mixed solution of ethanol and water at a ratio of 5:3(v/v), and weighing 3.223g of ZrOCl2·8H2And adding the O into the mixed solution for dissolving until the concentration of the O is 0.154mol/L, transferring the O into a wide-mouth bottle, sealing the wide-mouth bottle, and heating the wide-mouth bottle in a water bath kettle to 70 ℃ for heat preservation for 2 hours. The obtained clear and transparent zirconia sol is sealed and cooled to normal temperature for standby.
(2) Preparing a chitosan solution: firstly, preparing 1% glacial acetic acid by using high-purity water, weighing 0.176g of chitosan, adding a 1% glacial acetic acid solution to fully dissolve the chitosan, preparing 5.275g/L chitosan solution, then transferring the chitosan solution into a three-neck flask provided with a stirrer, stirring and continuously introducing nitrogen for 20min to ensure that the uniformly-mixed and oxygen-free chitosan solution is obtained.
(3) Preparing the chitosan stabilized zirconium modified nano ferrous sulfide composite material: weighing high-purity FeCl23.977g of the solution is dissolved in 100mL of high-purity water aerated with nitrogen, the solution is poured into a three-neck flask in a 30 ℃ constant-temperature water bath kettle containing the chitosan solution prepared in the step (2), nitrogen is continuously introduced (the flow rate is 500mL/min), and the mixture is stirred (the rotation speed is 300-400 rpm/min) for 15min, so that the FeCl which is uniformly mixed and is free of oxygen is obtained2A chitosan solution. Adding the 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, continuously introducing nitrogen after the dropwise addition is finished, stirring for 30min, and adding the obtained black suspension into N to obtain a black suspension2Transfer quickly to brown jars under protection. Standing for 24h after sealing to ensure that the nano particles fully grow, thereby obtaining the chitosan stabilized zirconium modified nano ferrous sulfide composite material (theoretical CS/ZrO)2-FeS＝0.1)。
Example 2
The embodiment provides a preparation method of a chitosan-stabilized zirconium-modified nano ferrous sulfide composite material (the molar ratio of zirconium oxide to ferrous sulfide is 1:2, and the mass ratio of chitosan to ferrous sulfide is 3:10), which comprises the following steps:
(1) the pretreatment of the zirconia sol was as described in step 1 of example 1.
(2) The chitosan solution was prepared as described in step 2 of example 1, except that 0.528g of chitosan was weighed.
(3) The preparation of the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material was the same as that described in step 3 of example 1. (theoretical CS/ZrO)2-FeS＝0.3)。
The rough, porous and rich zirconia component of the composite material obtained in the embodiment mainly exists in an amorphous state, and has strong adsorption capacity on metal ions. (as shown in fig. 1).
Example 3
The embodiment provides a preparation method of a chitosan-stabilized zirconium-modified nano ferrous sulfide composite material (the molar ratio of zirconium oxide to ferrous sulfide is 1:2, and the mass ratio of chitosan to ferrous sulfide is 5:10), which comprises the following steps:
(1) the pretreatment of the zirconia sol was as described in step 1 of example 1.
(2) The chitosan solution was prepared as described in step 2 of example 1, except that 0.88g of chitosan was weighed.
(3) The preparation of the zirconium chitosan modified nano ferrous sulfide composite material was the same as that described in step 3 of example 1. (theoretical CS/ZrO)2-FeS＝0.5)。
Comparative example
The present comparative example provides a method of preparing a nano ferrous sulfide material, the method comprising the steps of:
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 N2Transfer quickly to brown jars under protection. And standing for 24 hours after sealing to ensure that the nano particles fully grow, thereby obtaining the unmodified nano ferrous sulfide material.
The chitosan-stabilized zirconium-modified nano ferrous sulfide composite materials with different modification ratios (the mass ratios of chitosan to ferrous sulfide are 0.1, 0.3 and 0.5 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. 2, when the reaction reaches equilibrium, the removal rate of molybdenum at 10mg/L is slightly different for the three composite materials with chitosan modified ratio under the condition of initial pH value of 7. It can be seen that the material with the mass ratio of 0.3 is improved in molybdenum removal rate compared with the material with the mass ratio of 0.1, but the removal rate of the modified material with the mass ratio of 0.5 is obviously reduced, because the low-concentration chitosan can not play a space barrier role to cause the agglomeration of nano ferrous sulfide, and the high-concentration chitosan can increase the acidity of the system to decompose sodium sulfide, and the mass ratio of the selected chitosan to the ferrous sulfide is considered to be 0.3 comprehensively.
The chitosan-stabilized zirconium-modified nano ferrous sulfide composite material prepared in the example 2 and the nano ferrous sulfide material which is not modified in the comparative example are respectively used as adsorbents to treat molybdenum-containing wastewater simulated in a laboratory. The results of the experiment are shown in FIG. 3, and when the pH is increased from 4.0 to 10.0, the nano FeS is added to the MoO4 2-The removal rate of (C) is gradually reduced from 57.58% to 16.55%, while the removal rate of CS-ZrO is gradually reduced2The molybdenum removal rate of the/FeS is not changed greatly along with the increase of the pH value and is basically maintained to be more than 73.33 percent. Illustrates pH vs. MoO removal from pure FeS4 2-The composite material modified by adding the chitosan and the zirconia has high stability in a wide pH range.
The chitosan-stabilized zirconium-modified nano ferrous sulfide composite material prepared by the preparation method shown in example 2 and the nano ferrous sulfide material prepared in the comparative example were used for stability comparison experiments. The experimental results are shown in fig. 4, and it can be seen that the oxidation resistance and stability of the composite material are significantly improved. The chitosan stabilized zirconium modified nano ferrous sulfide composite material still has a removal rate of more than 78% on molybdenum-containing wastewater of 10mg/L when aged for 30d, and the removal rate of the pure ferrous sulfide nano material on molybdenum is reduced to about 19%.
The nano ferrous sulfide materials prepared in the above examples 1 to 3 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 16 hours, the water temperature was 25 ℃ and the shaking speed was 180 rpm.
The test data show that the adsorbing materials obtained in examples 1-3 of the present invention have very significant removal efficiency of molybdate from wastewater (as shown in table 1). The removal rate of molybdenum from the sorbent materials 1-3 was significantly higher than the removal rate of the comparative sorbent material at an initial pH of 7.
TABLE 1 results of the molybdenum removal experiments for the different examples
| Adsorbent and process for producing the same | Example 1 | Example 2 | Example 3 | Comparative example |
| Removal Rate (%) | 73.59 | 82.37 | 67.66 | 28.59 |
Claims (7)
1. A preparation method of a chitosan stabilized zirconium modified nano ferrous sulfide composite material 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 70 ℃ water bath kettle, and preserving heat for 2 hours to obtain clear and transparent zirconia sol and cooling the clear and transparent zirconia sol to normal temperature for later use;
the volume ratio of the ethanol to the water is 5: 3;
(2) preparing a 1-5% by mass percent diluted acid solution by using high-purity water, slowly adding chitosan, fully stirring and dissolving, and continuously introducing nitrogen to ensure that a uniformly mixed and oxygen-free chitosan solution is obtained;
(3) slowly adding the chitosan solution prepared in the step (2) into a ferrous salt aqueous solution prepared from deoxygenated water at 30 ℃ in a nitrogen atmosphere, continuously stirring for 15min in a three-neck flask provided with an electric stirrer, adding the zirconia sol prepared in the step (1), continuously stirring and continuously introducing nitrogen, uniformly stirring, dropwise adding a sodium sulfide aqueous solution prepared from the deoxygenated water at a fixed speed through a separating funnel, continuously stirring the mixed solution for 20-30 min after dropwise adding is finished, sealing and standing for 24-36 h to fully grow nanoparticles, thereby obtaining a chitosan-stabilized zirconium-modified nano ferrous sulfide composite material;
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; the mass ratio of the chitosan to the ferrous sulfide is 1: 10-1: 2.
2. The method for preparing the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the zirconium salt is ZrOCl2·8H2O。
3. The method for preparing the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the dilute acid is one of hydrochloric acid, nitric acid, acetic acid and benzoic acid.
4. The method for preparing the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the molar ratio of the ferrous salt to the sodium sulfide is 1: 1; the molar ratio of the zirconium oxide to the ferrous sulfide is 1: 2; the mass ratio of the chitosan to the ferrous sulfide is 3: 10.
5. Such asThe method for preparing the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material as claimed in claim 4, is characterized in that: the ferrous salt is FeCl2·4H2O。
6. The chitosan-stabilized zirconium-modified nano ferrous sulfide composite material obtained by the preparation method of any one of claims 1 to 5.
7. The application of the chitosan-stabilized zirconium-modified nano ferrous sulfide composite material of claim 6 in removing heavy metal molybdenum in water.
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