CN112028167B - High-iron clay composite material and preparation method and application thereof - Google Patents
High-iron clay composite material and preparation method and application thereof Download PDFInfo
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- CN112028167B CN112028167B CN202010908412.0A CN202010908412A CN112028167B CN 112028167 B CN112028167 B CN 112028167B CN 202010908412 A CN202010908412 A CN 202010908412A CN 112028167 B CN112028167 B CN 112028167B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
Abstract
The invention discloses a high-iron clay composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: purifying montmorillonite, carrying out montmorillonite sodium treatment, carrying out clay iron treatment, and preparing high-iron clay. The novel efficient environment-friendly water treatment agent prepared by the invention solves the problem of composite use of two environment-friendly materials, namely clay mineral and high-iron clay, fully exerts the advantages of the clay mineral and the high-iron clay, and has high economical efficiency, good activity and excellent environment compatibility.
Description
Technical Field
The invention belongs to the field of preparation of water treatment composite materials, and particularly relates to a high-iron clay composite material and a preparation method and application thereof.
Background
The clay mineral is used as an ecological environment material which is widely applied, and has rich resources, low price and low energy consumption. The minerals have good adsorption performance and can quickly adsorb pollutants. However, clay minerals do not convert pollutants such as organic pollutants in water into non-toxic and harmless substances because they do not have redox activity.
In recent years, iron-based materials made from iron and iron-containing minerals have also found wide use in the environment. The iron-based material is emphasized due to the advantages of large reserves in the earth, easy preparation, low price, environmental protection, efficient and quick treatment process and the like. Currently, zero valent iron and a wide variety of iron oxides, such as wustite (FeO), hematite (α -Fe)2O3) Maghemite (gamma-Fe)2O3) Magnetite (Fe)3O4) Goethite (alpha-FeOOH), wustite (gamma-FeOOH) and other forms of iron oxides or hydroxides (Fe (OOH)3，Fe(OOH)2，Fe(OH)2，Fe(OH)3) Are iron-based materials which are often mentioned and which rely mainly on adsorption for the removal of pollutants such as (heavy metals and organic pollutants) from water, while having a photocatalytic action driven by visible light, and which participate in photocatalytic degradation processes. Meanwhile, ferrate containing Fe (VI) has excellent oxidative degradation disinfection capability, and Fe (OH) is generated at the same time3Has good flocculation and precipitation effects, can adsorb toxic and harmful substances in water environment, and has no risk of disinfection byproducts such as ozone, chlorination and the like in the adding process.
However, in the practical use of ferrate, there are (1) poor stability: ferrate is active in property and is very easy to absorb moisture and lose activity in the processes of transportation and storage, so the ferrate is used for preparing more than once and is limited in use range; (2) the oxidative release is quick: when the ferrate reagent is added into a water body, the oxidation property of the ferrate reagent is quickly released, the effect is better in a short time, but the ferrate reagent cannot be maintained for a long time.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the high-iron clay composite material and the preparation method and the application thereof are provided for solving the problem of composite use of two environment-friendly materials of clay mineral and high-iron clay.
The technical scheme adopted by the invention is as follows:
the preparation method of the high-iron clay composite material comprises the following steps:
s1, adding water into raw montmorillonite ore, stirring for 2-3h, standing for 20-30h, centrifuging, removing supernatant and bottom impurities, retaining middle-layer solids, washing for 3-5 times with water, drying at 110 ℃, and crushing;
s2, adding sodium chloride and water into the montmorillonite crushed in the S1, reacting for 2-3h at 60-80 ℃, standing and cooling to room temperature, then centrifuging to remove supernatant and bottom impurities, retaining the middle layer, cleaning, and centrifuging again to remove supernatant to obtain clay;
s3, adding water into the clay obtained in the step S2, uniformly mixing to obtain a homogenate, dialyzing until chloride ions in the dialyzate are negative, drying at the temperature of 110 ℃, and grinding;
s4, adding FeCl into the montmorillonite treated by the S33Stirring the solution at a low speed for 20-30h, centrifuging, and removing supernatant; repeating the step S4 for 3-5 times, and then centrifuging to remove the supernatant and the bottom impurities to obtain clay;
s5, adding water into the clay obtained in the step S4, uniformly mixing to obtain a homogenate, dialyzing until chloride ions in the dialyzate are negative, and freeze-drying and grinding;
s6, adding anhydrous potassium carbonate solution into the calcium hypochlorite solution, supplementing water to maintain the system to be in a liquid state, adding potassium hydroxide solution, adding the clay obtained after the treatment of S5, stirring in an ice-water bath for 2-3 hours, standing for 30-45min, and centrifuging to obtain a crude product; washing the crude product with anhydrous ethanol and n-hexane in sequence, centrifuging to remove supernatant, and repeating washing and centrifuging for 3-5 times; and then freeze-drying to obtain the product.
The method comprises the steps of firstly, adding water into the montmorillonite raw ore, mixing, standing, centrifuging and purifying to remove partial impurities and improve the purity of clay minerals; then adding sodium chloride, mixing uniformly, centrifuging, and dialyzing to make montmorillonite sodium, so that montmorillonite has better ion exchange property, dispersion degree and physicochemical property than calcium magnesium montmorillonite; and adding a ferric ion solution, uniformly mixing and centrifuging to load ferric ions onto the interlayer domain of the sodium-based montmorillonite, and oxidizing the interlayer ferric ions of the montmorillonite into hexavalent iron ions in situ under a strong alkaline condition through free hypochlorite to complete the preparation of the high-iron clay. The prepared high-iron clay not only has high adsorbability of montmorillonite minerals, but also has strong oxidability of ferrate, and after hexavalent iron oxidizes organic matters, Fe (OH)3，Fe(OH)3The flocculant has good flocculation and precipitation effects, can adsorb toxic and harmful substances in water environment, and has no risk of disinfection byproducts such as ozone, chlorination and the like in the adding process; in addition, space junction between montmorillonite layersThe structure has the characteristic of slowly releasing hexavalent iron ions, thereby solving the stability problem of ferrate.
Further, the ratio of the raw montmorillonite ore to water in S1 is 40-60g:1L, preferably 50 g/L.
Further, centrifuging at 3000r/min for 5-10min in S1; centrifuging at 11000r/min for 5-10min in S2; centrifuging at 5000r/min for 5-10min in S4; and centrifuging at 5000r/min for 5-10min in S6.
Further, the ratio of montmorillonite, sodium chloride and water in S2 is 100g:50-70g:600-800mL, preferably 100g:60g:700 mL.
Further, the dialysis of S3 and S5 is specifically: dialyzing with 3500DA dialysis bag, and replacing dialysate every 4-6 h.
Further, in S4, a ferric ion solution with other anions can be used, and dialysis is performed during subsequent dialysis until the anions are negative.
Further, in S4, montmorillonite is in FeCl3The concentration of the solution is 90-110g/L, preferably 100 g/L.
Further, the concentration of the calcium hypochlorite solution in S6 is 400-600g/L, preferably 400 g/L; the concentration of the potassium carbonate solution is 300-500g/L, preferably 300 g/L; the concentration of the potassium hydroxide solution is 10-20mol/L, preferably 15 mol/L; the concentration of the clay is 10-30g/L, preferably 20 g/L; the volume ratio of the calcium chlorate solution, the potassium carbonate solution and the sodium hydroxide solution is 1.5-2.5:1.5-2.5:1, and preferably 2:2: 1.
Further, the montmorillonite and ground clay are both crushed and then sieved through a 200-mesh sieve.
The high-iron clay composite material is prepared by the method.
The application of the high-iron clay composite material in preparing the water treatment agent can be used as the water treatment agent for treating wastewater.
In conclusion, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the method, water is added to remove impurities and purify, so that part of impurities are removed, and the purity of clay minerals is improved; then sodium chloride is added to sodium montmorillonite, so that the montmorillonite has better ion exchange property, dispersion degree and physicochemical property than calcium magnesium montmorillonite; and adding an iron ion solution to load iron ions onto the interlayer domain of the sodium-based montmorillonite, and oxidizing trivalent iron ions between the montmorillonite layers into hexavalent iron ions in situ under the strong alkali condition through free hypochlorite to complete the preparation of the high-iron clay.
According to the invention, the clay mineral and the ferrate are compounded to prepare the novel high-iron clay composite material, on one hand, the addition of the clay mineral improves the physicochemical property and solves the problem that the ferrate is active and is easy to absorb moisture and inactivate, on the other hand, ferric ions loaded on the interlayer domain of the clay are oxidized into hexavalent iron ions in situ, so that the problem that the oxidative release is too fast after the ferrate is added is solved, and the application effect exertion time is prolonged. In addition, the clay mineral adsorption performance and the oxidation degradation capability of ferrate are combined, the clay mineral adsorption performance and the oxidation degradation capability of ferrate are fully utilized, and pollutants in water are removed by taking the clay mineral adsorption performance and the ferrate oxidation degradation capability as environment-friendly materials and taking the advantages that the risk of disinfection byproducts such as ozone and chlorination is avoided in the adding process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a FT-IR characterization chart of the product of this example 1;
FIG. 2 is an XRD characterization of the product of example 1;
FIG. 3 is an XPS profile of the product of example 1;
FIG. 4 is an SEM photograph of the product of example 1;
FIG. 5 is a graph of degradation curves.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preferred embodiment of the invention provides a preparation method of a high-iron clay composite material, which comprises the following specific steps:
(1) purification of montmorillonite: firstly, adding montmorillonite raw ore and pure water according to the solid-to-liquid ratio of 50g/L, stirring for 2.5h under the condition of 900r/min, and then standing for one day; centrifuging at 3000r/min for 5min, discarding supernatant and dark impurities at the bottom, and keeping intermediate yellow solid. Washing the yellow solid with water for 3 times, and drying at 105 deg.C; and finally, crushing by using a crusher and sieving by using a 200-mesh standard sieve for the next step.
(2) Carrying out montmorillonite sodium treatment: preparing purified 200-mesh-screened montmorillonite, sodium chloride and pure water, preparing a solution according to the proportion of 100g of montmorillonite, 60g of sodium chloride and 700mL of pure water, then reacting for 2h in a 70 ℃ water bath at 900r/min under stirring, standing, cooling to room temperature, centrifuging for 5min at 11000r/min, discarding supernatant and bottom dark impurities, taking the middle part, washing for 3 times by using pure water, and centrifuging for 5min at 11000r/min again to remove supernatant. Subsequently, the centrifuged clay was added to pure water to form a homogenate, which was dialyzed using 3500DA dialysis bags, with dialysate being changed every 5 h. When the detection of chloride ions in the dialysate is negative (no Tyndall effect is detected by 0.1M silver nitrate solution), drying and grinding at 105 ℃ to 200 meshes for later use.
(3) Iron-based treatment of clay: preparing 1mol/L Fe3+The solution was then concentrated to 1mol/L Fe at a concentration of 100g/L3+Adding sodium into the solution, adding montmorillonite sieved by 200 meshes, stirring at low speed for 24h, centrifuging for 5min under the condition of 5000r/min, removing supernatant, and repeating the step for 3 times; after the third time, the suspension is centrifuged for 5min at 5000r/min, and the supernatant and the bottom impurities are discarded. The centrifuged clay was then homogenized with pure water and dialyzed using 3500DA dialysis bags, replacing the dialysate every 5 h. In which Fe is added3+Slow formation of Fe (OH)3When using FeCl3When the iron is converted into iron, the solution is dialyzed to Cl-And (4) when the detection is negative (no Tyndall effect is detected by using 0.1M silver nitrate solution), freeze-drying the modified clay mineral, grinding and storing in a dryer.
(4) Preparing high-iron clay: preparing 100mL of 400G/L calcium hypochlorite solution, stirring at low speed for 30min, and performing suction filtration by using a G3 glass sand core funnel to remove insoluble substances and keep filtrate; slowly adding 100mL of anhydrous potassium carbonate of 300g/L into the filtrate under stirring, and supplementing a little pure water to maintain the volume of the system solution to be about 200 mL; then, carrying out suction filtration by adopting a G3 glass sand core funnel to obtain filtrate for later use; then preparing 15mol/L potassium hydroxide solution, and adding 50mL into the obtained filtrate after the solution is cooled; then adding iron-based clay into the solution to control the concentration of the iron-based clay to be 20g/L, stirring in ice water bath for 2 hours, standing for 30min, and centrifuging for 5min at 5000r/min to obtain a crude product; washing the crude product with anhydrous ethanol and n-hexane in sequence, centrifuging at 5000r/min to remove supernatant, and repeating the step for 3 times; washing, and freeze-drying to obtain Fe (VI) -clay-A.
FT-IR, XRD, XPS and SEM characterization are respectively carried out on the product prepared in the embodiment, and the results are shown in figures 1-4, and Fe (VI) -clay-A of the high-iron clay composite material is successfully prepared in the embodiment. From the infrared spectrum (figure 1), the synthesized high-iron clay has 1656cm of montmorillonite Si-O-Si skeleton characteristic peak-1And 1022cm-1And has ferrate (FeO)4 2-) Middle Fe-O bond characteristic peak 1404cm-1With FeO2 4-Characteristic peak 910cm-1(ii) a From the X-ray diffraction pattern (figure 2), the synthesized ferrate clay has a characteristic diffraction peak of ferrate, which shows that the synthesis of ferrate among montmorillonite layers is realized; from the XPS characterization result (figure 3), in the synthesized high-iron clay, a hexavalent iron ion peak is obvious; as can be seen from the scanning electron microscopy (fig. 4), in the synthesized ferrierite, potassium ferrate crystals were present between the montmorillonite layers.
Example 2
The preferred embodiment of the invention provides a preparation method of a high-iron clay composite material, which comprises the following specific steps:
(1) purification of montmorillonite: firstly, adding montmorillonite raw ore and pure water according to the solid-to-liquid ratio of 40g/L, stirring for 2.5h under the condition of 900r/min, and then standing for one day; centrifuging at 3000r/min for 5min, discarding supernatant and dark impurities at the bottom, and keeping intermediate yellow solid. Washing the yellow solid with water for 4 times, and drying at 105 deg.C; and finally, crushing by using a crusher and sieving by using a 200-mesh standard sieve for the next step.
(2) Carrying out montmorillonite sodium treatment: preparing purified 200-mesh-screened montmorillonite, sodium chloride and pure water, preparing a solution according to the proportion of 100g of montmorillonite, 60g of sodium chloride and 700mL of pure water, then reacting for 2h in a 70 ℃ water bath at 900r/min under stirring, standing, cooling to room temperature, centrifuging for 5min at 11000r/min, discarding supernatant and bottom dark impurities, taking the middle part, washing for 3 times by using pure water, and centrifuging for 5min at 11000r/min again to remove supernatant. Subsequently, the centrifuged clay was added to pure water to form a homogenate, which was dialyzed using 3500DA dialysis bags, with dialysate being changed every 5 h. When the detection of chloride ions in the dialysate is negative (no Tyndall effect is detected by 0.1M silver nitrate solution), drying and grinding at 105 ℃ to 200 meshes for later use.
(3) Clay iron amination: preparing 1mol/L Fe3+The solution was then concentrated to 1mol/L Fe at a concentration of 90g/L3 +Adding sodium into the solution, adding montmorillonite sieved by 200 meshes, stirring at low speed for 24h, centrifuging for 5min under the condition of 5000r/min, removing supernatant, and repeating the step for 3 times; after the third time, the suspension is centrifuged for 5min at 5000r/min, and the supernatant and the bottom impurities are discarded. The centrifuged clay was then homogenized with pure water and dialyzed using 3500DA dialysis bags, replacing the dialysate every 5 h. In which Fe is added3+Slow formation of Fe (OH)3When using FeCl3When the iron is converted into iron, the solution is dialyzed to Cl-And (4) when the detection is negative (no Tyndall effect is detected by using 0.1M silver nitrate solution), freeze-drying the modified clay mineral, grinding and storing in a dryer.
(4) Preparing high-iron clay: preparing 100mL of 500G/L calcium hypochlorite solution, stirring at low speed for 30min, and performing suction filtration by using a G3 glass sand core funnel to remove insoluble substances and keep filtrate; adding 100mL of anhydrous potassium carbonate of 400g/L slowly into the filtrate while stirring, and supplementing a little pure water to maintain the volume of the system solution at about 200 mL; then, carrying out suction filtration by adopting a G3 glass sand core funnel to obtain filtrate for later use; then preparing 15mol/L potassium hydroxide solution, and adding 50mL into the obtained filtrate after the solution is cooled; then adding iron-based clay into the solution to control the concentration of the iron-based clay to be 20g/L, stirring in ice water bath for 2 hours, standing for 30min, and centrifuging for 5min at 5000r/min to obtain a crude product; washing the crude product with anhydrous ethanol and n-hexane in sequence, centrifuging at 5000r/min to remove supernatant, and repeating the step for 3 times; and (4) after washing, freezing and drying to obtain the product.
Example 3
The preferred embodiment of the invention provides a preparation method of a high-iron clay composite material, which comprises the following specific steps:
(1) purification of montmorillonite: firstly, adding montmorillonite raw ore and pure water according to the solid-to-liquid ratio of 60g/L, stirring for 2.5h under the condition of 900r/min, and then standing for one day; centrifuging at 3000r/min for 5min, discarding supernatant and dark impurities at the bottom, and keeping intermediate yellow solid. Washing the yellow solid with water for 5 times, and drying at 105 deg.C; and finally, crushing by using a crusher and sieving by using a 200-mesh standard sieve for the next step.
(2) Carrying out montmorillonite sodium treatment: preparing purified 200-mesh-screened montmorillonite, sodium chloride and pure water, preparing a solution according to the proportion of 100g of montmorillonite, 60g of sodium chloride and 700mL of pure water, then reacting for 2h in a 70 ℃ water bath at 900r/min under stirring, standing, cooling to room temperature, centrifuging for 5min at 11000r/min, discarding supernatant and bottom dark impurities, taking the middle part, washing for 3 times by using pure water, and centrifuging for 5min at 11000r/min again to remove supernatant. Subsequently, the centrifuged clay was added to pure water to form a homogenate, which was dialyzed using 3500DA dialysis bags, with dialysate being changed every 5 h. When the detection of chloride ions in the dialysate is negative (no Tyndall effect is detected by 0.1M silver nitrate solution), drying and grinding at 105 ℃ to 200 meshes for later use.
(3) Clay iron amination: preparing 1mol/L Fe3+The solution was then concentrated to 1mol/L Fe at a concentration of 100g/L3+Adding sodium into the solution, adding montmorillonite sieved by 200 meshes, stirring at low speed for 24h, centrifuging for 5min under the condition of 5000r/min, removing supernatant, and repeating the step for 3 times; after the third time, the suspension is centrifuged for 5min at 5000r/min, and the supernatant and the bottom impurities are discarded. The centrifuged clay was then homogenized with pure water and dialyzed using 3500DA dialysis bags, replacing the dialysate every 5 h. In which Fe is added3+Slow formation of Fe (OH)3When using FeCl3When the iron is formed, it is necessary toDialyzing to Cl-And (4) when the detection is negative (no Tyndall effect is detected by using 0.1M silver nitrate solution), freeze-drying the modified clay mineral, grinding and storing in a dryer.
(4) Preparing high-iron clay: 100mL of 450G/L calcium hypochlorite solution is prepared, after stirring at low speed for 30min, a G3 glass sand core funnel is adopted for suction filtration, insoluble substances are removed, and filtrate is reserved; slowly adding 100mL of 350g/L anhydrous potassium carbonate into the filtrate under stirring, and supplementing a little pure water to maintain the volume of the system solution to be about 200 mL; then, carrying out suction filtration by adopting a G3 glass sand core funnel to obtain filtrate for later use; then preparing 15mol/L potassium hydroxide solution, and adding 50mL into the obtained filtrate after the solution is cooled; then adding iron-based clay into the solution to control the concentration of the iron-based clay to be 20g/L, stirring in ice water bath for 2 hours, standing for 30min, and centrifuging for 5min at 5000r/min to obtain a crude product; washing the crude product with anhydrous ethanol and n-hexane in sequence, centrifuging at 5000r/min to remove supernatant, and repeating the step for 3 times; and (4) after washing, freezing and drying to obtain the product.
Examples of the experiments
The performance test of the high iron clay composite material Fe (VI) -clay-A prepared in example 1 is carried out. Example 1 degradation tests were carried out with the first generation cephalosporin-typical drug Cefazolin sodium (CFZ) as dependent variable, with the addition of material (0.1g) and the addition of equivalent potassium ferrate (0.1 g). Sampling every 30min, filtering with 0.45 μm glass fiber filter membrane, dropping 2-3 drops of 0.1mol/L sodium thiosulfate to terminate the reaction, and storing in a 2 ml brown chromatographic bottle to be tested. The primary application of the Fe (VI) -clay-A composite material is shown in FIG. 5, wherein the concentration is used as an ordinate and the sampling time is used as an abscissa. According to the figure, on one hand, the synthesized ferric clay and potassium ferrate have equivalent effect to potassium ferrate materials when the adding amount is the same; on the other hand, the oxidative release of the synthesized high-iron clay is slower than that of ferrate in the early reaction stage, which shows that the synthesized high-iron clay has a slow release effect and is beneficial to improving the stability of potassium ferrate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The preparation method of the high-iron clay composite material is characterized by comprising the following steps of:
s1, adding water into montmorillonite raw ore, stirring for 2-3h, standing for 20-30h, centrifuging to remove supernatant and bottom impurities, retaining middle layer solids, washing with water for 3-5 times, drying at 110 ℃, crushing, and sieving with a 200-mesh sieve;
s2, adding sodium chloride and water into the montmorillonite treated in the S1, reacting for 2-3h at 60-80 ℃, standing and cooling to room temperature, centrifuging to remove supernatant and bottom impurities, reserving the middle layer, cleaning, and centrifuging again to remove the supernatant to obtain clay;
s3, adding water into the clay obtained in the step S2, uniformly mixing to obtain a homogenate, dialyzing until chloride ions in the dialyzate are negative, drying at the temperature of 110 ℃, grinding, and sieving with a 200-mesh sieve;
s4, adding FeCl into the montmorillonite treated by the S33Stirring the solution at a low speed for 20-30h, centrifuging, and removing supernatant; repeating the step S4 for 3-5 times, and then centrifuging to remove the supernatant and the bottom impurities to obtain clay;
s5, adding water into the clay obtained in the step S4, uniformly mixing to obtain a homogenate, dialyzing until chloride ions in the dialyzate are negative, freeze-drying, grinding, and sieving with a 200-mesh sieve;
s6, adding anhydrous potassium carbonate solution into the calcium hypochlorite solution, supplementing water to maintain the system to be in a liquid state, adding potassium hydroxide solution, adding the clay obtained after the treatment of S5, stirring in an ice-water bath for 2-3 hours, standing for 30-45min, and centrifuging to obtain a crude product; washing the crude product with anhydrous ethanol and n-hexane in sequence, centrifuging to remove supernatant, and repeating washing and centrifuging for 3-5 times; and then freeze-drying to obtain the product.
2. The method for preparing a high-iron clay composite material according to claim 1, wherein the ratio of the raw montmorillonite to water in S1 is 40-60g: 1L.
3. The method for preparing a high-iron clay composite material as claimed in claim 1, wherein the centrifugation condition in S1 is 3000r/min for 5-10 min; centrifuging for 5-10min at 11000r/min in the S2; centrifuging for 5-10min at the centrifugation condition of 5000r/min in the S4; and the centrifugation condition in the S6 is 5000r/min for 5-10 min.
4. The method for preparing a high-iron clay composite material as claimed in claim 1, wherein the ratio of montmorillonite, sodium chloride and water in S2 is 100g:50-70g:600-800 mL.
5. The method for preparing a high-iron clay composite material as claimed in claim 1, wherein the dialyzing step of S3 and S5 comprises: dialyzing with 3500DA dialysis bag, and replacing dialysate every 4-6 h.
6. The method for preparing high-iron clay composite material according to claim 1, wherein the montmorillonite in S4 is FeCl3The concentration of the solution is 90-110 g/L.
7. The method for preparing a high-iron clay composite material as claimed in claim 1, wherein the concentration of the calcium hypochlorite solution in S6 is 400-600g/L, the concentration of the potassium carbonate solution is 300-500g/L, the concentration of the potassium hydroxide solution is 10-20mol/L, and the concentration of the clay is 10-30 g/L; the volume ratio of the calcium chlorate solution, the potassium carbonate solution and the sodium hydroxide solution is 1.5-2.5:1.5-2.5: 1.
8. The high iron clay composite material prepared by the method of any one of claims 1 to 7.
9. Use of the high iron clay composite material of claim 8 in the preparation of a water treatment agent.
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